total synthesis of (±)-pallambins c and d · supplementary information for total synthesis of...
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Supplementary Information for
Total Synthesis of (±)-Pallambins C and D
Xue-Song Xu, Zhen-Wu Li, Yi-Jun Zhang, Xiao-Shui Peng, and Henry N. C. Wong*
Table of contents General information……………………………………………………………………………….S2
Synthesis of compound 6………………………………………………………………………….S3
Synthesis of compound 6a………………………………………………………….......................S4
Synthesis of compound 7………………………………………………………………………….S4
Synthesis of compound 8………………………………………………………………………….S5
Synthesis of compound 9………………………………………………………………………….S5
Synthesis of compound 9a………………………………………………………….......................S6
Synthesis of compound 9b………………………………………………………….......................S6
Synthesis of compound 10………………………………………………………….......................S7
Synthesis of compound 10a……………………………………………………….........................S7
Synthesis of compound 11………………………………………………………….......................S8
Synthesis of compound 12………………………………………………………….......................S9
Synthesis of compound 12a……………………………………………………………………….S9
Synthesis of compound 13……………………………………………………………………….S10
Synthesis of compound 13a……………………………………………………….......................S10
Synthesis of compound 14……………………………………………………………………….S11
Synthesis of compound 14a……………………………………………………….......................S11
Synthesis of compound 15……………………………………………………………………….S12
Synthesis of compound 15b……………………………………………………….......................S13
Synthesis of compound 16……………………………………………………………………….S13
Synthesis of compound 16a……………………………………………………….......................S14
Synthesis of compound 4………………………………………………………...........................S14
Synthesis of compound 17……………………………………………………….........................S15
Synthesis of compound 17a……………………………………………………….......................S15
Synthesis of compound 18……………………………………………………………………….S16
Synthesis of compound 19……………………………………………………………………….S16
Synthesis of compound 20……………………………………………………………………….S17
Synthesis of compound 21……………………………………………………………………….S17
Synthesis of compound 22……………………………………………………………………….S18
Synthesis of compound 23……………………………………………………………………….S18
Synthesis of compound 24……………………………………………………………………….S19
Synthesis of compound 25……………………………………………………………………….S19
Synthesis of compound 26……………………………………………………………………….S20
Synthesis of compound 27……………………………………………………………………….S20
Synthesis of compound 26a……………………………………………………….......................S21
Synthesis of pallambin C (1)…………………………………………………………………….S22
Synthesis of compound 27a……………………………………………………….......................S22
Synthesis of pallambin D (2)……………………………………………………….....................S23
NMR spectra and basic crystal data…………..…………………….....................................S24-S70
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General Information
Unless stated otherwise, all reactions were carried out under an argon atmosphere under anhydrous conditions and all reagents were purchased from commercial suppliers without further purification. Solvent drying by standard methods were employed when necessary. The plates used for thin-layer chromatography (TLC) were E. Merck silica gel 60F254 (0.24 nm thickness) precoated on aluminum plates, and then visualized under UV light (365 nm and 254 nm) or through staining with a 5% of dodecamolybdophosphoric acid in ethanol and subsequent heating. Column chromatography was performed using E. Merck silica gel (230-400 mesh). Melting points were measured on an Electrothermal 9100 apparatus without correction. NMR spectra were recorded on a Bruker Advance III 400 spectrometer (400.00 MHz for 1H and 100 MHz for 13C) and a Bruker 400 MHz NMR AV400Q (400.00 MHz for 1H and 100 MHz for 13C) at room temperature. Solvent signal was used as reference for 1H, 13C NMR (CDCl3, 7.26, 77.16 ppm; C6D6, 7.16, 128.06 ppm). The following abbreviations were used to explain the multiplicities: s = singlet, d = doublet, t = triplet, q = quartet, brs = broad singlet, dd = double doublet, td = triple doublet, dt = double triplet, dq = double quartet, m = multiplet. Mass spectra (ESI, EI and FAB) were obtained with a ThermoFinnigan MAT 95 XL spectrometer and determined at an ionized voltage of 70 eV unless otherwise mentioned. Elemental analyses were performed at Shanghai Institute of Organic Chemistry, The Chinese Academy of Sciences, China. Infrared spectra (IR) were recorded on a Perkin Elmer (Spectrum One) FT-IR spectrometer.
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Experimental details and characteristic data for compounds
From Wieland-Miescher ketone to 11
OAcH
O
11
EtO
EtO
i, j
OH
HOHOAc
OH
HO
OBn
BnOO
OBn
BnOOH
OBn
BnO
6 7
89
O
O
Wieland-Miescher ketone
a b,c
10
f,g, h
d
e
X-ray structures of 10 (left) and 11 (right)
Synthesis of compound 6
To a stirred solution of (±)-Wieland-Miescher ketone (12.0 g, 67.4 mmol) and CeCl3•7H2O (37.6 g, 101 mmol) in MeOH (250 mL) at -78 °C was added NaBH4 (5.1 g, 13.5 mmol) in one portion. The reaction was stirred for 20 min at -78 °C and warmed up to rt, filtered through Celite. The filtered cake was washed with MeOH (200 mL x 2). After evaporation, the residue was partitioned between EA (500 mL) and saturated NH4Cl (500 mL), and the aqueous phase was extracted with EA (300 mL x 3). The combined organic phase was dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silical gel, Hex/EA = 2:1) to afford 6 (10.6 g, 86%) as a white solid. mp 151.0-152.0 oC. 1H NMR (400 MHz, CDCl3) δ = 5.41 (s, 1H), 4.18 (brs, 1H), 3.29-3.24 (m, 1H), 2.18-2.10 (m, 1H), 2.01-1.93 (m, 2H), 1.86-1.75 (m, 3H), 1.61-1.54 (m, 1H), 1.48-1.43 (m, 4H), 1.34-1.23 (m, 1H), 1.07 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ = 144.92, 126.06, 79.22, 67.79, 40.76, 33.64, 31.46, 30.85, 29.00, 24.71, 16.92 ppm; IR (neat) 2934, 2860, 1658, 1445, 1050, 931 cm-1; HRMS (EI) m/z Calcd for C11H18O2 [M]+: 182.1301, found 182.1306.
Synthesis of compound 6a
To a stirred solution of compound 6 (14.2 g, 78 mmol) in DMF (160 mL) at was
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added NaH (~60%, 12.5 g, 312 mmol) in portions 0 °C. The formed mixture was stirred for 30 min at the same temperature, and then BnBr (28 mL, 234 mmol) was added dropwise during 15 min. The reaction was allowed to warm to rt and stirred for 20 h. The reaction mixture was pre-cooled in ice bath and quenched with water (500 mL), extracted with EA (300 mL x 2), washed with brine (300 mL), dried over Na2SO4, concentrated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 100:1-50:1) to afford 6a (26.8 g, 95%) as a colorless oil. 1H NMR (400 MHz, CDCl3) δ = 7.38-7.27 (m, 10H), 5.49 (s, 1H), 4.66 (d, J = 11.9 Hz, 1H), 4.62 (d, J = 11.9 Hz, 1H), 4.56 (d, J = 12.0 Hz, 1H), 4.43 (d, J = 11.9 Hz, 1H), 3.97-3.94 (m, 1H), 2.98 (dd, J = 4.2, 11.6 Hz, 1H), 2.21-2.15 (m, 1H), 2.04-1.96 (m, 4H), 1.82-1.79 (m, 1H), 1.60-1.54 (m, 2H), 1.38-1.31 (m, 1H), 1.26-1.17 (m, 1H), 1.15 (s, 3H); 13C NMR δ = (100 MHz, CDCl3) δ = 145.59, 139.40, 139.14, 128.45, 128.35, 127.81, 127.56, 127.54, 127.45, 123.39, 86.46, 74.48, 71.44, 70.05, 41.13, 34.07, 31.78, 26.74, 25.35, 24.63, 17.99 ppm;. IR (neat) 2937, 2860, 1658, 1453, 1358, 1094, 1070, 734, 696 cm-1; HRMS (EI) m/z Calcd for C25H30O2 [M]+: 362.2240, found 362.2254.
Synthesis of compound 7
To a well stirred suspension of compound 6a (19.7 g, 54.4 mmol) and NaHCO3 (20 g, 238.1 mmol) in DCM (500 mL) was added mCPBA (~70%, 20 g, 81.4 mmol). The reaction was stirred for 3 h at rt, and then was partitioned with water (500 mL). The aqueous phase was extracted with DCM (300 mL), and the combined organic phase was washed with saturated NaHCO3 (300 mL) and brine (300 mL), dried over Na2SO4, evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 40:1-20:1) to afford 7 (17.7 g, 86%) as a colorless oil. 1H NMR (400 MHz, CDCl3) δ = 7.38-7.27 (m, 10H), 4.65 (d, J = 11.1 Hz, 1 H), 4.63 (s, 2 H), 4.44 (d, J = 11.8 Hz, 1 H), 3.72 (dd, J = 7.8, 8.1 Hz, 1 H), 3.37-3.33 (m, 1H), 3.04 (s, 1H), 2.04-1.98 (m, 2H), 1.94-1.89 (m, 1H), 1.76-1.73 (m, 1H), 1.65-1.56 (m, 3H), 1.53-1.43 (m, 1H),1.32-1.24 (m, 1H), 1.19 (s, 3H), 0.96 (d, J = 14.4 Hz, 1H) ppm; 13C NMR (100 MHz, CDCl3) δ = 139.31,138.33, 128.58, 128.35, 127.86, 127.53, 127.46, 83.69, 72.70, 71.68, 71.32, 66.62, 61.53, 38.88, 29.14, 27.56, 26.48, 24.07, 20.74, 16.25 ppm; IR (neat) 2948, 2868, 1605, 1497, 1454, 1360, 1093, 1073, 738, 702 cm-1; HRMS (ESI) m/z Calcd for C25H30O3Na [M+Na]+: 401.2087, found 401.2100; Anal. Calcd for C25H30O3: C, 79.33; H, 7.99; found C, 79.28; H, 8.15.
Synthesis of compound 8
OBn
BnOO
OBn
BnOOH
8
CH3MgI
benzene, reflux, 12 h
7
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To a stirred solution of MeMgI in minimized amount of Et2O [prepared from Mg turnings (5.5 g, 230 mmol) and MeI (13.7 mL, 220 mmol), and distilled off most of the solvent Et2O] was added a solution of the epoxide above (16.8 g, 44.4 mmol) in benzene (300 mL), and the reaction was stirred under reflux for 12 h. After being cooled to 0 °C, the reaction was quenched with 5% HCl (500 mL), extracted with EA (300 mL x 2). The combined organic phase was washed with saturated NaHCO3 (300 mL) and brine (300 mL), dried over Na2SO4, evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 20:1-10:1) to afford 8 (15.6 g, 89%) as a colorless oil. 1HNMR (400 MHz, CDCl3) δ = 7.37-7.27 (m, 10H), 4.61 (d, J = 11.8 Hz, 1H), 4.55 (d, J = 11.9 Hz, 1H), 4.49 (d, J = 11.9 Hz, 1H), 4.44 (d, J = 11.8 Hz, 1H), 4.09-4.04 (m, 1H), 3.56 (dd, J = 4.5, 11.5 Hz, 1H), 2.12-1.96 (m, 2H), 1.89-1.60 (m, 8H), 1.52-1.42 (m, 1H), 1.09 (s, 3H), 1.05 (d, J = 7.6 Hz, 3H), 0.74 (s, 1H) ppm; 13C NMR (100 MHz, CDCl3) δ = 139.72, 139.32, 128.45, 128.31, 127.55, 127.47, 127.45, 127.32, 82.12, 78.91, 76.60, 71.89, 69.96, 45.71, 42.42, 32.81, 30.35, 26.26, 23.52, 19.05, 15.26, 10.33 ppm; IR (neat) 2939, 2867, 1496, 1453, 1386, 1364, 1095, 1071, 953, 735, 698 cm-1; HRMS (ESI) m/z Calcd for C26H34O3Na [M+Na]+: 417.2400, found 417.2390; Anal. Calcd for C26H34O3: C, 79.15; H, 8.69; found C, 78.96; H, 8.92.
Synthesis of compound 9
To a stirred solution of compound 8 (18.3 g, 46.4 mmol) and pyridine (100 mL) in DCM (250 mL) at 0 °C was added a solution of SOCl2 (10 mL, 138 mmol) in DCM (50 mL) dropwise during 10 min. The reaction was stirred for 30 min at the same temperature and quenched with ice water (500 mL). The aqueous phase was extracted with DCM (300 mL), and the combined organic phase was washed with 5% HCl (300 mL) and brine (300 mL), dried over Na2SO4, evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 100:1-50:1) to afford 9 (16.1 g, 92%) as a colorless oil. 1H NMR (400 MHz, CDCl3) δ = 7.42-7.32 (m, 10H), 5.42 (brs, 1H), 4.75 (d, J = 11.9 Hz, 1H), 4.65 (d, J = 11.9 Hz, 1H), 4.54 (d, J = 12.1 Hz, 1H), 4.50 (d, J = 12.0 Hz, 1H), 3.50-3.45 (m, 1H), 3.19 (dd, J = 3.1, 12.2 Hz, 1H), 2.91-2.84 (m, 1H), 2.25-2.10 (m, 3H), 2.00-1.68 (m, 4H), 1.28 (s, 3H), 1.26 (d, J = 7.5 Hz, 3H), 1.15 (dt, J = 3.9, 13.5 Hz, 1H) ppm; 13C NMR (100 MHz, CDCl3) δ = 145.67, 139.42, 139.19, 128.39, 128.28, 127.47, 127.40, 127.34, 122.34, 85.61, 79.91, 71.20, 69.66, 41.55, 39.29, 36.53, 25.17, 23.19, 22.72, 20.64, 16.55 ppm; IR (neat) 2940, 2870, 1605, 1496, 1454, 1363, 1099, 1074, 1028, 734, 696 cm-1; HRMS (ESI) m/z Calcd for C26H32O2Na [M+Na]+: 399.2295, found 399.2286.
Synthesis of compound 9a
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OBn
BnO
9
OBn
BnOHOH
9a
1) BH3.Me2S, Et2O,
RT, 20 h
2) NaOH, H2O2, THF,RT, 10 h
To a stirred solution of compound 9 (14.7 g, 39.1 mmol) in Et2O (400 mL) was added BH3•Me2S (neat, 8 mL, 80 mmol) dropwise during 10 min. The reaction was stirred for 20 h at rt, and then was added water/THF (1:1,100 mL) slowly at -10 °C. NaOH (3M, 100 mL) and 30% H2O2 (50 mL) were added successively, and the formed mixture was stirred for 10 h at rt. Cooled to 0 °C, saturated Na2S2O3 was added dropwise during 30 min, and the stirring continued for 30 min. The aqueous phase was extracted with Et2O (300 mL), and the combined organic phase was washed with saturated NH4Cl (300 mL) and brine (300 mL), dried over Na2SO4, evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 5:1) to afford 9a (12.6 g, 82%) as a colorless oil. 1H NMR (400 MHz, CDCl3) δ = 7.38-7.28 (m, 10H), 4.63 (d, J = 11.8 Hz, 1H), 4.61 (d, J = 11.8 Hz, 1H), 4.48 (d, J = 11.9 Hz, 1H), 4.41 (d, J = 11.8 Hz, 1H), 3.82 (dt, J = 4.1, 10.4 Hz, 1H), 3.42-3.37 (m, 1H), 2.89 (dd, J = 4.0, 11.4 Hz, 1H), 2.69-2.65 (m, 1H), 2.13-2.09 (m, 1H), 2.04-2.00 (m, 1H), 1.95-1.91 (m, 1H), 1.74-1.68 (m, 2H), 1.57-1.47 (m, 2H), 1.33-1.23 (m, 1H), 1.07-1.04 (m, 2H), 1.03 (d, J = 7.4 Hz, 3H), 1.01 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ = 139.25, 139.17, 12844, 128.33, 127.58, 127.46, 86.88, 80.59, 71.49, 69.61, 66.96, 51.45, 39.43, 37.01, 34.23, 30.28, 24.97, 23.27, 14.72, 9.14 ppm; IR (neat) 2936, 2856, 1637, 1453, 1384, 1363, 1073, 1027, 735, 697 cm-1; HRMS (ESI) m/z Calcd for C26H34O3Na [M + Na]+: 417.2400, found 417.2391; Anal. Calcd for C26H34O3: C, 79.15; H, 8.69; found C, 78.61; H, 9.07.
Synthesis of compound 9b
OBn
BnO
OAcH
9b
OBn
BnOHOH
9a
Ac2O, Py, DMAP
DCM, RT, 1 h
To a stirred solution of compound 9a (12.6 g, 32 mmol), pyridine (3.5 mL) and DMAP (0.5 g) in DCM (50 mL) was added Ac2O (3.6 mL, 35 mmol) dropwise during 5 min at 0 °C. The reaction was stirred for 1 h at rt, and then was quenched with ice water (100 mL). The aqueous phase was extracted with DCM (100 mL), and the combined organic phase was washed with 5% HCl (100 mL x 2) and brine (100 mL x 2), dried over Na2SO4, evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 10:1) to afford 9b (13.8 g, 99%) as a white solid. mp 80.5-81.8 °C. 1H NMR (400 MHz, CDCl3) δ = 7.36-7.27 (m, 10H), 5.01 (dt, J = 4.8, 11.1 Hz, 1H), 4.61 (d, J = 12.2 Hz, 1H), 4.58 (d, J = 13.0 Hz, 1H), 4.51 (d, J = 11.9 Hz, 1H), 4.41 (d, J = 11.8 Hz, 1H), 3.41-3.36 (m, 1H), 2.90 (dd, J = 4.0 , 11.5 Hz, 1H), 2.44-2.40 (m, 1H), 2.21-2.16 (m, 1H), 2.08-2.03 (m, 1H), 2.05 (s, 3H), 1.95-1.91 (m, 1H), 1.76-1.66 (m, 2H), 1.62-1.51 (m, 1H), 1.35-1.21 (m, 2H), 1.09-1.01 (m, 1H),1.04 (s, 3H), 0.91 (d, J = 7.4 Hz, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ = 170.70,
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139.21, 139.15, 128.45, 128.36, 127.54, 127.50, 86.46, 80.59, 71.49, 70.10, 69.86, 48.88, 39.75, 36.90, 30.84, 30.31, 24.69, 22.97, 21.35, 14.59, 9.13 ppm; IR (neat) 2940, 2861, 1735, 1454, 1365, 1244, 1098, 1075, 1027, 735, 698 cm-1; HRMS (ESI) m/z Calcd for C28H36O4Na [M + Na]+ 459.2506, found 459.2496; Anal. Calcd for C28H36O4: C, 77.03; H, 8.31; found C, 76.72; H, 8.14.
Synthesis of compound 10
To a solution of compound 9b (18.5 g, 42.4 mmol) in EtOH (500 mL) was added Pd/C (10%, 2 g), and the reaction was stirred for 20 h at rt under an atmosphere of H2. The reaction mixture was filtered through Celite and washed with MeOH (500 mL), then concentrated and purified by a flash column (silica gel, Hex/EA = 2:1) to afford 10 (10.3 g, 95%) as a white solid. mp 168.7- 170.1 °C. The structure of 10 was confirmed by X-ray crystallographic results. 1H NMR (400 MHz, CDCl3) δ = 4.97 (dt, J = 4.8 Hz, 11.2 Hz, 1H), 3.71-3.66 (m, 1H), 3.21 (dd, J = 3.6, 11.3 Hz, 1H), 2.29-2.25 (m, 1H), 2.15-2.11 (m, 1H), 2.02 (s, 3H), 1.83 (td, J = 3.2, 13.2 Hz, 1H), 1.74-1.70 (m, 1H), 1.66-1.63 (m, 2H), 1.45-1.28 (m, 4H), 1.18-1.10 (m, 1H), 0.94 (s, 3H), 0.87 (d, J = 7.4 Hz, 3H) ppm; 13C NMR (100MHz, CDCl3) δ = 170.75, 79.26, 73.69, 69.79, 48.57, 38.93, 36.53, 33.64, 30.32, 28.62, 25.69, 21.28, 13.45, 8.59 ppm; IR (neat) 2931, 2869, 1735, 1712, 1639, 1242, 1057, 1015 cm-1; HRMS (ESI) m/z Calcd for C14H24O4Na [M + Na]+ 279.1567, found 279.1569; Anal. Calcd for C14H24O4: C, 65.60; H, 9.44; found C, 65.39; H, 9.30.
Synthesis of compound 10a
To a stirred solution of compound 10 (9.6 g, 37.5 mmol) in acetone (400 mL) at 0 °C was added Jones’ reagent dropwise [prepared from CrO3 (27 g) and conc. H2SO4 (23 mL), and diluted to 100 mL with water] until TLC indicated the starting material was consumed completely. The reaction was quenched with iPrOH (10 mL) and filtered through Celite. The filtered cake was washed with acetone (400 mL). After concentration, the residue was partitioned between DCM (500 mL) and water (300 mL). The aqueous phase was extracted with DCM (200 mL x 2). The combined organic phase was washed with saturated NaHCO3 (200 mL ) and brine (200 mL), dried over Na2SO4, evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 6:1-3:1) to afford 10a (8.7 g, 92%) as a colorless oil, and revealed by 1H NMR a mixture of the C-4 methyl diastereomers with a α/β ratio of 7:3. mp 61.4-65.2 °C. 1H NMR (400 MHz, CDCl3) δ = 5.36 (dt, J = 4.5, 11.0 Hz,
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0.7H), 5.18 (td, J = 5.6, 9.4 Hz, 0.3H), 2.83-2.33 (m, 6H), 2.19-1.74 (m, 6H), 1.65-1.58 (m, 1H), 1.40 (s, 1.93 H), 1.31 (s, 0.85H), 1.16 (d, J = 7.8 Hz, 1.93 H), 1.09 (d, J = 6.8 Hz, 0.85 H) ppm; 13C NMR (100 MHz, CDCl3) δ = 213.16, 211.24, 170.60, 71.80, 67.99, 50.68, 48.68, 46.61, 46.28, 45.02, 44.28, 36.02, 35.18, 34.52, 34.05, 32.49, 30.79, 29.39, 21.57, 21.12, 19.20, 17.84, 14.07 ppm; IR (neat) 2954, 1736, 1711, 1458, 1429, 1379, 1241, 1062, 1030 cm-1; HRMS (EI) m/z Calcd for C14H20O4 [M]+ 252.1356, found 252.1345; Anal. Calcd for C14H20O4: C, 66.65; H, 7.99; found C, 66.23; H, 7.81.
Synthesis of compound 11
To a stirred solution of compound 10a (7.8 g, 31 mmol) in EtOH (150 mL) was added CH(OEt)3 (3.5 mL, 21 mmol) and pTsOH•H2O (150 mg, 0.8 mmol). The reaction was stirred for 30 min at rt, and then quenched with saturated NaHCO3 (150 mL), extracted with DCM (300 mL x 2). The combined organic phase was washed with brine (200 mL x 2), dried over Na2SO4, and evaporated to give a residue, which was purified by flash column (silica gel, Hex/EA = 10:1-5:1) to afford 11 (6.2 g, 61%, 90% brsm) as a white solid, and recovered dione (2.5 g, 32%). mp 83.5-85.0 °C. 1H NMR (400 MHz, CDCl3) δ = 5.27 (dt, J = 4.7, 11.1 Hz, 1H), 3.44-3.32 (m, 4H), 2.67 (dt, J = 6.7, 14.6, 1H), 2.35-2.19 (m, 3H), 2.08 (dd, J = 4.5, 11.9, 1H), 2.04 (s, 3H), 1.86-1.42 (m, 5H), 1.17 (s, 3H), 1.12 (t, J = 6.6 Hz, 6H), 0.92 (d, J = 7.5 Hz, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ = 212.79, 170.71, 101.82, 68.76, 54.92, 54.70, 47.04, 45.75, 35.35, 35.25, 30.93, 29.53, 23.91, 21.23, 19.68, 15.39, 15.29, 11.48 ppm; IR (neat) 2974, 1738, 1714, 1639, 1378, 1238, 1097, 1048, 1033 cm-1; HRMS (EI) m/z Calcd for C18H30O5 [M]+ 326.2088, found 326.2090; Anal. Calcd for C18H30O5: C, 66.23; H, 9.26; found C, 66.29; H, 9.39.
Synthesis of compound 12
To a solution of compound 11 (7.9 g, 24.2 mmol) in MeOH (200 mL) was added K2CO3 (2 g), and the formed mixture was stirred for 4 h at rt. The reaction was quenched with saturated NH4Cl (100 mL), and extracted with DCM (250 mL x 3). The combined organic phase was washed with brine (100 mL), dried over Na2SO4, and evaporated under vacuum to give 11a as white solid, which was dissolved in EtOH (30 mL), and then was added dropwise to a stirred solution of hydrazine monohydrate (20 mL) and Et3N (20 mL) in EtOH (10 mL). The solution was stirred under reflux for 3 h. After evaporation, the residue was partitioned between EA (200
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mL) and water (50 mL), and the aqueous phase was extracted with EA (100 mL x 3). The combined organic phase was washed with brine (50 mL), dried over Na2SO4, evaporated and dried under vacuum to give the hydrazone as a white solid, which was then used directly for the next process. To a stirred solution of I2 (19 g, 75 mmol) in THF (80 mL) was added a solution of TMG (1,1,3,3-tetramethylguanidine) (20 mL, 160 mmol) in THF (80 mL) dropwise during 30 min at rt, and then a solution of the above hydrazone in THF (80 mL) was added dropwise during 10 min. The reaction was stirred at rt for 10 min, cooled and quenched with saturated Na2S2O3 (100 mL), partitioned between EA (300 mL) and water (100 mL). The aqueous phase was extracted with EA (200 mL), and the combined organic phase was washed with brine (100 mL x 2), dried over Na2SO4, evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA/Et3N = 20:1:0.01) to afford 12 (8.0 g, 84%) as a pale yellow syrup. 1H NMR (400 MHz, C6D6) δ = 5.89 (dd, J = 2.8, 5.1 Hz, 1H), 3.58 (brs, 1H ), 3.43-3.35 (m, 3H), 3.21-3.17 (m, 1H), 2.57-2.54 (m, 1H), 2.19 (dd, J = 4.4, 11.6, 1H), 2.01-1.93 (m, 1H), 1.74-1.71 (m, 1H), 1.63-1.55 (m, 3H), 1.51-1.47 (m, 1H), 1.11 (t, J = 7.1 Hz, 3H), 1.05 (t, J = 7.0 Hz, 3H), 0.94-0.92 (m, 6H) ppm; 13C NMR (100 MHz, C6D6) δ = 134.71, 117.85, 102.88, 64.39, 55.05, 54.95, 48.15, 42.99, 40.98, 39.90, 34.68, 25.66, 20.80, 15.57, 15.52, 11.52 ppm; IR (neat) 2971, 2926, 1645, 1634, 1449, 1385, 1086, 1049 cm-1; HRMS (EI) m/z Calcd for C16H27IO3 [M]+ 394.0999, found 394.0986.
Synthesis of compound 12a
OHH
I
12
EtO
EtO
1) BnBr, NaH,DMF, 0 oC~r.t, 20 h
2) (CH2OH)2, pTsOH.H2O,
benzene, reflux, 20 hOBn
H
I
12a
O
O
To a stirred solution of compound 12 (4 g, 10 mmol) in DMF (40 mL) at 0 °C was added NaH (~60%, 2 g, 50 mmol) in portions. After stirring for 30 min, BnBr (3.5 mL, 29 mmol) was added dropwise during 5 min. The reaction was warmed up to rt and stirred for 20 h. Cooled to 0 °C, the reaction was quenched with water (40 mL), extracted with EA (100 mL x 2), washed with saturated NH4Cl (100 mL) and brine (100 mL), dried over Na2SO4, evaporated and dried under vacuum to give a residue, which was used directly for the next process. The residue above was dissolved in benzene (100 mL), followed by addition of ethylene glycol (4 mL) and pTsOH•H2O (400 mg, 2.1 mmol). The reaction was stirred under reflux for 20 h with the Dean-Stark apparatus to remove water formed, and then cooled to rt, partitioned between EA (100 mL) and water (100 mL). The organic phase was washed with saturated NaHCO3 (100 mL) and brine (100 mL), dried over Na2SO4, evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 50:1-30:1) to afford 12a (4.1 g, 89%) as a pale yellow semi-solid. 1H NMR (400 MHz, CDCl3) δ = 7.37-7.27 (m, 5H), 6.17 (dd, J = 2.8, 5.2 Hz, 1H), 4.64 (d, J = 11.4 Hz, 1H), 4.42 (d, J = 11.4 Hz, 1H), 3.97-3.88 (m, 4H), 3.77-3.70 (m, 1H), 2.66 (td, J = 5.6, 17.2 Hz, 1H), 2.32-2.26 (m, 2H), 2.12 (dq, J = 2.8, 8.8 Hz, 1H), 1.89-1.81 (m, 1H), 1.65-1.61 (m, 1H), 1.57-1.49 (m, 2H), 1.03 (s,
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3H), 0.97 (d, J = 7.3 Hz, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ = 138.54, 134.05, 128.49, 127.86, 127.77, 117.25, 111.57, 71.36, 71.02, 64.48, 64.23, 47.58, 42.34, 40.20, 37.40, 36.15, 27.62, 20.72, 12.01 ppm; IR (neat) 2945, 2881, 1453, 1373, 1355, 1099, 736, 698 cm-1; HRMS (ESI) m/z Calcd for C21H28IO3 [M+H]+ 455.1078, found 455.1085.
Synthesis of compound 13
A suspension of compound 12a (4.5 g, 10 mmol), Pd(OAc)2 (225 mg , 1 mmol) and Et3N (5.5 mL, 40 mmol) in MeOH/DMF (64 mL, 7/1) was degassed and charged with CO (balloon), stirred at 55 °C for 24 h. The reaction mixture was cooled to rt, diluted with EA (100 mL) and filtered through Cellite. The filtrate was washed with water (50 mL), saturated NH4Cl (50 mL) and brine (50 mL). The organic phase was collected, dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 50:1-20:1) to afford 13 (3.1 g, 81%) as a white solid. mp 99.5-100.2 °C. 1H NMR (400 MHz, CDCl3) δ = 7.35-7.27 (m, 5H), 6.59 (dd, J = 3.1, 4.6 Hz, 1H), 4.67 (d, J = 11.4 Hz, 1H), 4.45 (d, J = 11.4 Hz, 1H), 3.96-3.87 (m, 4H), 3.79-3.73 (m, 1H), 3.68 (s, 3H), 2.85 (td, J = 5.4, 18.9 Hz, 1H), 2.42-2.36 (m, 1H), 2.34-2.29 (m, 1H), 2.19 (dq, J = 3.0, 8.5 Hz, 1H), 2.03 (dd, J = 4.6, 11.5 Hz, 1H), 1.93 (ddd, J = 3.1, 4.1, 5.2 Hz, 1H ), 1.52-1.44 (m, 2H), 1.27 (s, 3H), 1.02 (d, J = 7.5 Hz, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ = 167.28, 140.62, 138.67, 135.19, 128.50, 127.86, 127.75, 111.37, 71.41, 71.04, 64.39, 64.17, 51.38, 47.56, 38.05, 36.09, 33.89, 33.09, 27.05, 21.20, 12.18 ppm; IR (neat) 2981, 2950, 2882, 1714, 1435, 1359, 1239, 1101, 1077, 737, 699 cm-1; HRMS (ESI) m/z Calcd for C23H31O5 [M+H]+ 387.2166, found 387.2163. Anal. Calcd for C23H30O5: C, 71.48; H, 7.82; found C, 71.49; H, 7.84.
Synthesis of compound 13a
To a solution of compound 13 (3 g, 7.8 mmol) in DCM (30 mL) at -78 °C was added DIBAL-H solution (15 mL, 1 M in toluene) dropwise during 5 min, and the reaction was stirred at the same temperature for 20 min. The reaction was quenched with saturated NH4Cl (20 mL), diluted with DCM (50 mL) and water (50 mL). The organic phase was washed with brine (50 mL x 2), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 2:1) to afford 13a (2.7 g, 97%) as a white solid. mp 109.7-110.7 °C. 1H NMR (400 MHz, CDCl3) δ = 7.35-7.27 (m, 5H), 5.54-5.52 (m, 1H), 4.67 (d, J = 11.4 Hz, 1H), 4.43 (d, J = 11.4
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Hz, 1H), 4.13-4.06 (m, 2H), 3.97-3.88 (m, 4H), 3.81-3.74 (m, 1H), 2.81-2.74 (m, 1H), 2.40-2.33 (m, 1H), 2.13-2.05 (m, 2H), 1.92 (dt, J = 5.0, 13.3 Hz, 1H), 1.73-1.66 (m, 2H), 1.55-1.49 (m, 1H), 1.22 (brs, 1H), 1.13 (s, 3H), 1.01 (d, J = 7.5 Hz, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ = 146.33, 138.87, 128.45, 127.86, 127.64, 119.91, 111.49, 72.17, 70.75, 64.36, 64.18, 62.72, 47.19, 37.98, 36.15, 33.46, 33.25, 26.98, 21.93, 12.14 ppm; IR (neat) 2929, 2883, 1454, 1383, 1355, 1092, 988 cm-1; HRMS (ESI) m/z Calcd for C22H31O4 [M+H]+ 359.2217, found 359.2245. Anal. Calcd for C22H30O4: C, 73.71; H, 8.44; found C, 73.36; H, 8.96.
Synthesis of compound 14
To a stirred solution of compound 13a (2.7 g, 7.5 mmol), DIPEA (6 mL, 36 mmol) and DMAP (10 mg) in toluene (50 mL) was added MOMCl (2.3 mL, 30 mmol) dropwise during 5 min at rt. The reaction was stirred at 70 °C for 20 h and then allowed to rt. The reaction was quenched with water (50 mL), extracted with EA (100 mL x 2), washed with saturated NaHCO3 (50 mL) and brine (50 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 20:1-10:1) to afford 14 (2.9 g, 96%) as a pale yellow oil. 1H NMR (400 MHz, CDCl3) δ = 7.35-7.28 (m, 5H), 5.55 (brs, 1H), 4.67 (d, J = 11.4 Hz, 1H), 4.61 (s, 2H), 4.42 (d, J = 11.4 Hz, 1H), 4.03 (d, J = 12.3 Hz, 1H), 3.96-3.88 (m, 5H), 3.81-3.75 (m, 1H), 3.36 (s, 3H), 2.77 (td, J = 5.5, 17.5 Hz, 1H), 2.39-2.33 (m, 1H), 2.12-2.05 (m, 2H), 1.92 (dt, J = 5.2, 13.0 Hz, 1H), 1.71-1.65 (m, 2H), 1.52 (dd, J = 1.7, 13.5 Hz, 1H), 1.10 (s, 3H), 1.01 (d, J = 7.5 Hz, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ = 142.70, 138.89, 128.43, 127.87, 127.62, 122.09, 111.51, 95.65, 72.11, 70.71, 67.20, 64.35, 64.18, 55.50, 47.15, 37.95, 36.13, 33.47, 33.36, 27.00, 21.69, 12.15 ppm; IR (neat) 2923, 2883, 1725, 1454, 1382, 1358, 1098, 698 cm-1; HRMS (ESI) m/z Calcd for C24H34O5Na [M+Na]+ 425.2298, found 425.2294.
Synthesis of compound 14a
To a stirred solution of compound 14 (2.6 g, 6.5 mmol) in Et2O (60 mL) was added BH3•Me2S (neat, 1.3 mL, 13 mmol) dropwise during 10 min. The reaction was stirred for 20 h at rt, and then was added water/THF (1:1, 20 mL) slowly at -10 °C. NaOH (3M, 20 mL) and 30% H2O2 (10 mL) were added successively, and the resultant mixture was stirred for 10 h at rt. Cooled to 0 °C, saturated Na2S2O3 was added dropwise during 30 min, and the stirring continued for additional 30 min. The aqueous phase was extracted with Et2O (100 mL), and the combined organic phase
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was washed with saturated NH4Cl (100 mL) and brine (100 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 10:1-2:1) to afford 14a (2.1 g, 77%) as a colorless oil. 1H NMR (400 MHz, C6D6) δ = 7.32-7.30 (m, 2H), 7.18-7.15 (m, 2H), 7.10-7.06 (m, 1H), 4.53 (d, J = 11.4 Hz, 1H), 4.29 (s, 2H), 4.16 (d, J = 11.5 Hz, 1H), 3.87-3.80 (m, 1H), 3.70 (dd, J = 3.2, 9.9 Hz, 1H), 3.57-3.36 (m, 6H), 3.34 (d, J = 2.7 Hz, 1H), 3.09 (s, 3H), 2.77 (td, J = 4.6, 11.8 Hz, 1H), 2.68-2.61 (m, 1H), 2.05 (dd, J = 4.8, 11.2 Hz, 1H), 1.89 (ddd, J = 4.6, 4.1, 3.6 Hz, 1H), 1.65-1.46 (m, 4H), 1.39-1.34 (m, 1H), 1.12 (d, J = 7.6 Hz, 3H), 0.67 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 139.63, 128.54, 128.00, 127.59, 111.39, 96.65, 73.08, 70.53, 69.80, 67.78, 64.25, 64.08, 56.00, 55.18, 50.77, 41.60, 36.72, 36.39, 36.22, 27.14, 16.65, 12.55 ppm; IR (neat) 2934, 2884, 1453, 1386, 1148, 1101, 1030, 924, 698 cm-1; HRMS (ESI) m/z Calcd for C24H36O6Na [M+Na]+ 443.2404, found 443.2424.
Synthesis of compound 15
To a stirred solution of compound 14a (2 g, 4.8 mmol), pyridine (1 mL) and DMAP (100 mg) in DCM (20 mL) was added Ac2O (0.7 mL, 7.1 mmol) at 0 °C. The reaction was warmed up to rt and stirred for 2 h, and then quenched with water (20 mL). The aqueous phase was extracted with DCM (50 mL), and the combined organic phase was washed with 5% HCl (50 mL) and brine (50 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 7:1-5:1) to afford 15 (2.1 g, 95%) as a white solid. mp 92.7-94.0 °C. 1H NMR (400 MHz, C6D6) δ = 7.30-7.28 (m, 2H), 7.18-7.14 (m, 2H), 7.09-7.06 (m, 1H), 5.27 (dt, J = 5.0, 11.5 Hz, 1H), 4.45-4.39 (m, 3H), 4.05 (d, J = 11.5 Hz, 1H), 3.58 (d, J = 3.5 Hz, 2H), 3.52-3.39 (m, 5H), 3.17 (s, 3H), 2.83 (td, J = 4.8, 11.3 Hz, 1H), 2.64-2.58 (m, 1H), 2.03 (dd, J = 4.8, 11.2 Hz, 1H), 1.95 (dt, J = 5.8, 12.6 Hz, 1H), 1.80 (s, 3H), 1.70-1.66 (m, 2H), 1.55-1.38 (m, 3H), 1.10 (d, J = 7.6 Hz, 3H), 0.90 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 169.94, 139.53, 128.55, 127.59, 111.41, 96.81, 73.07, 70.80, 69.61, 64.49, 64.24, 64.08, 55.03, 54.43, 50.74, 38.20, 36.78, 36.62, 36.52, 27.10, 20.94, 16.83, 12.36 ppm; IR (neat) 2946, 2885, 1733, 1369, 1245, 1149, 1101, 1029, 698 cm-1; HRMS (ESI) m/z Calcd for C26H38O7Na [M+Na]+ 485.2510, found 485.2517.
Synthesis of compound 15b
OBnH
15
O
O
MOMO
OAcMsCl, Et3N,Pd/C, H2,
EtOH,50 oC, 4 h OH
H
O
O
MOMO
OAc
15a
DCM,-78 oC, 40 min OMs
H
O
O
MOMO
OAc
15b To a solution of compound 15 (2 g, 4.3 mmol) in EtOH (50 mL) was added Pd/C (200
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mg, 10%). The reaction was degassed and charged with H2 (balloon), stirred at 50 °C for 4 h. Cooled to rt, the reaction mixture was diluted with EA (200 mL), filtered through Celite. The filtrate was concentrated and the residue was dried under vacuum to give 15a as a colorless oil, which was used directly for the next process. To a stirred solution of compound 15a and Et3N (3 mL) in DCM (40 mL) was added MsCl (0.6 mL, 7.5 mmol) dropwise during 10 min at -78 °C. The reaction was stirred at the same temperature for 40 min, and then quenched with water (20 mL), extracted with DCM (30 mL x 2). The combined organic phase was washed with brine (40 mL x 2), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 7:1-5:1) to afford 15b (1.8 g, 92%) as a white solid. mp. 109.5-110.7 °C. 1H NMR (400 MHz, C6D6) δ = 5.15 (dt, J = 5.0, 11.5 Hz, 1H), 5.15 (dt, J = 5.1, 11.3 Hz, 1H), 4.37 (d, J = 6.4 Hz, 1H), 4.33 (d, J = 6.5 Hz, 1H), 3.50-3.44 (m, 6H), 3.12 (s, 3H), 2.99-2.94 (m, 1H), 2.32-2.30 (m, 1H), 2.27 (s, 3H), 2.01 (dd, J = 4.6, 11.6 Hz, 1H), 1.85-1.77 (m, 1H), 1.75 (s, 3H), 1.66-1.53 (m, 3H), 1.43-1.29 (m, 2H), 1.20 (d, J = 7.6 Hz, 3H), 0.65 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 169.69, 110.93, 96.68, 76.88, 68.60, 64.29, 64.17, 55.03, 53.99, 49.58, 39.50, 38.87, 36.87, 36.71, 36.38, 26.59, 20.76, 16.10, 12.06 ppm; IR (neat) 2944, 2879, 1735, 1451, 1342, 1244, 1174, 1150, 1100, 1032, 931, 903 cm-1; HRMS (ESI) m/z Calcd for C20H34O9SNa [M+Na]+ 473.1816, found 473.1810.
Synthesis of compound 16
OMsH
MOMO
OAc
O
OMsH
O
O
MOMO
OAc
15b
PPTS, acetone/H2O,
reflux, 24 h
16
A solution of compound 15b (1.7 g, 3.8 mmol) and PPTS (100 mg, 0.4 mmol) in acetone/water (30 mL, 9/1) was stirred under reflux for 24 h. Cooled to rt, the reaction mixture was partitioned between EA (100mL) and water (50 mL), washed with saturated NaHCO3 (50 mL) and brine (50 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 3:2) to afford 16 (1.3 g, 85%) as a white solid. mp. 118.5-121.2 °C. 1H NMR (400 MHz, C6D6) δ = 5.07 (dt, J = 5.0, 11.5 Hz, 1H), 4.80 (dt, J = 5.1, 11.2 Hz, 1H), 4.34 (d, J = 6.4 Hz, 1H), 4.30 (d, J = 6.5 Hz, 1H), 3.38-3.31 (m, 2H), 3.11 (s, 3H), 3.05-2.99 (m, 1H), 2.76-2.69 (m, 1H), 2.20-2.11 (m, 1H), 2.15 (s, 3H), 2.03-1.99 (m, 1H), 1.72 (s, 3H), 1.60-1.53 (m, 2H), 1.34 (dd, J = 5.8, 11.4 Hz, 1H), 1.06 (d, J = 7.7 Hz, 3H), 1.03-0.95 (m, 2H), 0.50 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 210.87, 169.47, 96.72, 74.97, 68.07, 64.10, 55.11, 53.31, 50.75, 43.70, 39.32, 38.62, 37.96, 36.54, 33.80, 20.66, 15.50, 13.44 ppm; IR (neat) 2936, 2891, 1732, 1709, 1336, 1242, 1172, 1151, 1045, 931, 905 cm-1; HRMS (ESI) m/z Calcd for C18H30O8SNa [M+Na]+ 429.1554, found 429.1541; Anal. Calcd for C18H30O8S: C, 53.19; H, 7.44; found C, 53.55; H, 7.20.
Synthesis of compound 16a
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OMsH
MOMO
OAc
O
OMsH
MOMO
OAc
O
1) PhSeCl, pTsOH.H2OEA, 0 oC, 2.5 h
2) Py, H2O2,DCM, 0 oC, 45 min
16a16
To a stirred solution of compound 16 (1.3 g, 3.2 mmol) in EA (35 mL) at 0 °C was added PhSeCl (0.6 g, 4.8 mmol) and pTsOH•H2O (67 mg, 0.35 mmol). The reaction was stirred at the same temperature for 2.5 h, and then diluted with DCM (35 mL), followed by addition of pyridine (1.5 mL) and H2O2 (30%, 1.5 mL). The stirring continued at 0 °C for 45 min, and aqueous CuSO4 (10%, 15 mL) was added. The resultant mixture was stirred for additional 10 min, diluted with water (50 mL), extracted with DCM (50 mL x 2). The combined organic phase was washed with saturated Na2S2O3 (50 mL), 5% HCl (50 mL) and brine (50 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 3:2) to afford 16a (0.92 g, 71%) as a white solid. mp 93.8-95.4 °C. 1H NMR (400 MHz, C6D6) δ = 6.77 (d, J = 10.4 Hz, 1H), 5.86 (d, J = 10.4 Hz, 1H), 4.97 (dt, J = 5.2, 11.4 Hz, 1H), 4.84 (dt, J = 5.1, 11.2 Hz, 1H), 4.33 (d, J = 6.5 Hz, 1H), 4.28 (d, J = 6.5 Hz, 1H), 3.41 (d, J = 4.2 Hz, 2H), 3.09 (s, 3H), 3.03-2.97 (m, 1H), 2.82-2.74 (m, 1H), 2.20 (s, 3H), 1.76-1.72 (m, 1H), 1.69 (s, 3H), 1.54-1.46 (m, 1H), 1.40-1.35 (m, 1H), 1.21 (d, J = 7.8 Hz, 3H), 0.57 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 199.81, 169.49, 154.48, 126.65, 96.60, 74.15, 67.79, 63.93, 55.20, 49.75, 48.92, 39.76, 39.19, 39.12, 38.47, 20.59, 17.64, 13.83 ppm; IR (neat) 2938, 2890, 1736, 1676, 1338, 1240, 1176, 1031, 936 cm-1; HRMS (ESI) m/z Calcd for C18H29O8S [M+H]+ 405.1578, found 405.1611; Anal. Calcd for C18H28O8S: C, 53.45; H, 6.98; found C, 53.74; H, 6.88.
Synthesis of compound 4
OMsH
MOMO
OAc
O
516aOMs
H
MOMO
OH
O
K2CO3
MeOH, RT, 3 h
tBuOK, tBuOH,
70 oC, 15 min
OH
OMOM
O4
To a solution of compound 16a (800 mg, 2 mmol) in MeOH (20 mL) was added K2CO3 (200 mg). The reaction was stirred for 3 h at rt, and then partitioned between EA (50 mL) and water (20 mL), extracted with EA (20 mL x 2). The combined organic phase was washed with brine (20 mL), dried over Na2SO4, evaporated and dried under vacuum to give 5 as a white solid (700 mg, 98%), which was used directly for the next process. To a stirred solution of compound 5 in tBuOH (20 mL) was added tBuOK (2.4 g, 21 mmol) rapidly. The reaction was stirred at 70 °C for 15 min, and then cooled at an ice bath, quenched with saturated NH4Cl (20 mL), partitioned between EA (50 mL) and water (20 mL). The aqueous phase was extracted with EA (50 mL), and the combined organic phase was washed with brine (20 mL x 2), dried over Na2SO4, evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 3:1-2:1) to afford 4 (0.32 g, 61%) as a white semi-solid. 1H NMR (400 MHz, C6D6) δ = 6.33 (dd,
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J = 1.8, 9.6 Hz, 1H), 6.04 (d, J = 9.6 Hz, 1H), 5.58 (td, J = 10.2, 16.7 Hz, 1H), 4.98-4.92 (m, 2H), 4.43 (s, 2H), 4.06 (brs, 1H), 3.58 (dd, J = 5.4, 10.0 Hz, 1H), 3.48-3.44 (m, 2H), 3.16 (s, 3H), 2.37 (d, J = 9.6 Hz, 1H), 2.06 (dd, J = 5.0, 9.1 Hz, 1H), 1.38 (s, 3H), 0.88 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 200.78, 158.44, 134.07, 128.34, 120.16, 96.93, 81.94, 67.80, 64.26, 60.89, 55.36, 54.86, 46.09, 18.67, 18.45 ppm; IR (neat) 2964, 2930, 1668, 1455, 1382, 1150, 1110, 1061, 919 cm-1; HRMS (ESI) m/z Calcd for C15H22O4Na [M+Na]+ 289.1410, found 289.1429.
Synthesis of compound 17
To a solution of compound 4 (300 mg, 1.1 mmol) in DCM (15 mL) was added DMP (700 mg, 1.7 mmol). The reaction was stirred at rt for 40 min, and then was quenched with saturated Na2S2O3 (10 mL), extracted with DCM (20 mL x 2). The combined organic phase was washed with saturated NaHCO3 (20 mL) and brine (20 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 4:1) to afford 17 (268 mg, 90%) as a colorless oil. 1H NMR (400 MHz, C6D6) δ = 6.03 (dd, J = 2.2, 9.6 Hz, 1H), 5.72-5.62 (m, 2H), 5.05-4.99 (m, 2H), 4.21 (s, 2H), 3.80 (dd, J = 4.1, 10.1 Hz, 1H), 3.31 (dd, J = 2.4, 10.2 Hz, 1H), 3.11 (dd, J = 2.0, 9.4 Hz, 1H), 3.04 (s, 3H), 1.92 (dd, J = 2.4, 4.0 Hz, 1H), 1.45 (s, 3H), 0.94 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 210.67, 192.45, 157.85, 132.70, 127.06, 121.43, 96.51, 69.47, 65.25, 64.52, 55.28, 54.97, 44.01, 17.85, 13.79 ppm; IR (neat) 2932, 2884, 1747, 1681, 1450, 1373, 1151, 1112, 1033, 920 cm-1; HRMS (ESI) m/z Calcd for C15H20O4Na [M+Na]+ 287.1254, found 287.1254.
Synthesis of compound 17a
To a stirred solution of compound 17 (400 mg, 1.5 mmol) and CeCl3•7H2O (840 mg, 2.3 mmol) in MeOH (15 mL) at -78 °C was added NaBH4 (60 mg, 1.5 mmol) in portions during 15 min, and the stirring continued for 5 min at the same temperature. The reaction was quenched with saturated NH4Cl (10 mL), extracted with EA (30mL x 2). The combined organic phase was washed with brine (20 mL x 2), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 4:1-1:1) to afford 17a (181 mg, 45%) as a colorless oil. Other generated isomers were mixed and oxidized to the starting material diketone, which was used again for this reduction. After three recycles, the desired alcohol 17a (314 mg, total 78%) was obtained. 1H NMR (400 MHz, C6D6) δ = 6.17 (td, J = 9.9 , 17.1 Hz, 1H), 5.58 (dd, J = 3.7, 9.6 Hz, 1H), 5.46 (d, J = 9.5 Hz, 1H), 5.13 (dd, J = 2.2,
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17.1 Hz, 1H), 5.06 (dd, J = 2.4 , 10.2 Hz, 1H), 4.25 (s, 2H), 3.74 (dd, J = 4.6, 10.0 Hz, 1H), 3.66-3.64 (m, 1H), 3.34 (dd, J = 2.5, 10.0 Hz, 1H), 3.08 (s, 3H), 2.82 (d, J = 9.7 Hz, 1H), 2.01 (dd, J = 2.5, 4.6 Hz, 1H), 1.41 (d, J = 7.2 Hz, 1H), 1.29 (s, 3H), 1.04 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 219.71, 140.82, 135.90, 127.82, 118.55, 96.49, 70.63, 65.68, 58.94, 57.10, 56.24, 55.18, 42.72, 18.37, 16.46 ppm; IR (neat) 2962, 2929, 2874, 1738, 1451, 1373, 1150, 1106, 1049, 1013, 917 cm-1; HRMS (ESI) m/z Calcd for C15H22O4Na [M+Na]+ 289.1410, found 289.1405.
Synthesis of compound 18
To a stirred solution of compound 17a (330 mg, 1.2 mmol) and Et3N (0.7 mL, 5.0 mmol) in DCM (10 mL) at ice-salt bath was added TBSOTf (0.8 mL, 3.5 mmol) dropwise during 5 min. The reaction was allowed to warm to 0 °C and stirred under argon atmosphere for 3 h, and then quenched with saturated NaHCO3 (5 mL).The aqueous phase was extracted with DCM (20 mL), and the combined organic phase was washed with brine (20 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 40:1) to afford 18 (424 mg, 90%) as a colorless oil. 1H NMR (400 MHz, C6D6) δ = 6.40 (td, J = 10.3 , 16.6 Hz, 1H), 5.51 (s, 2H), 5.15 (dd, J = 2.3, 8.5 Hz, 1H), 5.12 (s, 1H), 4.28 (s, 2H), 3.83 (s, 1H), 3.78 (dd, J = 4.8, 10.0 Hz, 1H), 3.42 (dd, J = 2.4, 10.0 Hz, 1H), 3.11 (s, 3H), 2.85 (d, J = 10.0 Hz, 1H), 2.10 (dd, J = 2.4, 4.7 Hz, 1H), 1.34 (s, 3H), 1.11 (s, 3H), 0.94 (s, 9H), -0.01(s, 3H), -0.04 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 219.83, 140.49, 136.89, 127.82, 117.06, 96.56, 70.80, 65.75, 59.29, 57.18, 55.20, 42.87, 25.92, 18.48, 18.23, 17.34, 1.41, -4.35, -5.00 ppm; IR (neat) 2957, 2930, 2885, 2858, 1742, 1691, 1473, 1463, 1253, 1151, 1066, 883, 777 cm-1; HRMS (ESI) m/z Calcd for C21H36O4SiNa [M+Na]+ 403.2275, found 403.2297.
Synthesis of compound 19
To a stirred mixture of Mg (192 mg, 8 mmol) and TiCl4 (0.21 mL, 2 mmol) in DCM (4 mL) at 0 °C was added a solution of compound 18 (380 mg, 1 mmol) in DCM/THF (3 mL/2 mL) dropwise during 2 min. The reaction was stirred for 45 min at 0 °C under argon atmosphere, and the resulting green-black mixture was stirred for additional 25 min at rt. The reaction mixture was re-cooled to 0 °C, and then quenched with saturated K2CO3 (2 mL), diluted with EA (50 mL), filtered through Celite. The filtrate was washed with saturated NaHCO3 (20 mL) and brine (20 mL), dried over Na2SO4, evaporated to give a residue, which was purified by a flash
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column (silica gel, Hex/EA = 40:1-20:1) to afford 19 (291 mg, 77%) as a colorless oil. 1H NMR (400 MHz, C6D6) δ = 6.37 (td, J = 10.1, 17.0 Hz, 1H), 5.58 (s, 2H), 5.16-5.06 (m, 4H), 4.45 (s, 2H), 3.70 (s, 1H), 3.58 (dd, J = 6.8, 10.0 Hz, 1H), 3.43 (dd, J = 4.7, 10.2 Hz, 1H), 3.18 (s, 3H), 2.61-2.59 (m, 1H), 2.29 (d, J = 10.0 Hz, 1H), 1.29 (s, 3H), 1.14 (s, 3H), 0.99 (s, 9H), 0.06(s, 3H), 0.03 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 159.58, 139.47, 138.20, 127.82, 116.19, 110.00, 96.81, 75.73, 70.10, 58.28, 55.15, 54.76, 51.11, 44.54, 26.03, 21.40, 19.48, 18.29, -4.07, -4.88 ppm; IR (neat) 2956, 2929, 2858, 1635, 1251, 1151, 1112, 1064, 1042, 886, 836, 774 cm-1; HRMS (ESI) m/z Calcd for C22H38O3SiNa [M+Na]+ 401.2482, found 401.2501.
Synthesis of compound 20
To a solution of compound 19 (240 mg, 0.63 mmol) in butanone/water (5mL/0.5 mL) was added NaI (286 mg, 1.9 mmol) and PPTS (240 mg, 0.95 mmol). The reaction was stirred under reflux for 20 h, and then cooled to rt, partitioned between EA (20 mL) and water (20 mL), extracted with EA (10 mL x 2). The combined organic phase was washed with saturated NaHCO3 (10 mL) and brine (10 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA =20:1-10:1) to afford 20 (119 mg, 56%) as a colorless oil. 1H NMR (400 MHz, C6D6) δ = 6.33 (td, J = 10.1, 17.0 Hz, 1H), 5.57-5.50 (m, 2H), 5.13-5.01 (m, 4H), 3.66 (d, J = 3.1 Hz, 1H), 3.51-3.45 (m, 1H), 3.33-3.28 (m, 1H), 2.35-2.32 (m, 1H), 2.21 (d, J = 10.0 Hz, 1H), 1.23 (s, 3H), 1.03 (s, 3H), 0.99 (s, 9H), 0.05(s, 3H), 0.02 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 159.48, 139.45, 138.04, 127.63, 116.23, 109.83, 75.78, 63.92, 58.26, 51.21, 44.45, 26.01, 21.26, 19.14, 18.28, -4.08, -4.90 ppm; IR (neat) 2957, 2929, 2857, 1635, 1251, 1060, 885, 836, 774 cm-1; HRMS (EI) m/z Calcd for C20H34O2Si [M]+ 334.2323, found 334.2324.
Synthesis of compound 21
To a stirred solution of compound 20 (100 mg, 0.3 mmol) and VO(acac)2 (1.6 mg, 0.006 mmol) in benzene (3 mL) was added TBHP (5.5 M in decane, 66 μL, 0.36 mmol) at rt. The reaction was stirred for 4 h, and then diluted with EA (20 mL). The solution was washed with saturated NaHCO3 (10 mL) and brine (10 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA =15:1) to afford 21 (90 mg, 86%) as a colorless oil. 1H NMR (400 MHz, C6D6) δ = 6.20 (td, J = 10.1, 17.0 Hz, 1H), 5.50-5.43 (m, 2H), 5.08-5.00 (m, 2H), 3.71-3.65 (m, 1H), 3.53 (d, J = 3.4 Hz, 1H), 3.50-3.44 (m, 1H), 2.46 (dd, J = 5.6,
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8.3 Hz, 1H), 2.41 (d, J = 10.0 Hz, 1H), 2.33 (d, J = 4.5 Hz, 1H), 2.28 (d, J = 4.5 Hz, 1H), 1.82 (dd, J = 3.9, 7.5 Hz, 1H), 0.95 (s, 9H), 0.94 (s, 3H), 0.93 (s, 3H), 0.01(s, 3H), -0.02 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 139.59, 137.32, 126.69, 116.77, 72.84, 69.17, 61.46, 58.10, 53.26, 48.67, 48.52, 44.15, 25.95, 19.09, 18.24, 16.09, -4.03, -4.97 ppm; IR (neat) 2958, 2929, 1635, 1256, 1063, 837, 774 cm-1; HRMS (ESI) m/z Calcd for C20H34O3SiNa [M+Na]+ 373.2169, found 373.2170.
Synthesis of compound 22
To a stirred solution of compound 21 (80 mg, 0.23 mmol) in Et2O (8 mL) was added LAH (43 mg, 1.1 mmol) at rt. The reaction was stirred under reflux for 7 h. After being cooled to 0 °C, the reaction was quenched with Na2SO4•10 H2O (5 g) in portions and stirred for additional 2 h at rt, filtered. The filtered cake was washed with EA (10 mL x 3), and the combined filtrate was evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA =10:1-5:1) to afford 22 (72 mg, 90%) as a white solid. mp 91.0-92.0 °C. 1H NMR (400 MHz, C6D6) δ = 6.27 (td, J = 10.2, 16.9 Hz, 1H), 5.50 (dd, J = 3.6, 9.4 Hz, 1H), 5.45 (dd, J = 1.2, 9.6 Hz, 1H), 5.10-5.04 (m, 2H), 3.79 (d, J = 3.5 Hz, 1H), 3.64-3.58 (m, 1H), 3.55-3.50 (m, 1H), 2.48 (d, J = 10.1 Hz, 1H), 2.12 (s, 1H), 1.88 (t, J = 5.3 Hz, 1H), 1.62 (dd, J = 4.3, 9.0 Hz, 1H), 1.14 (s, 3H), 1.07 (s, 3H), 1.00 (s, 9H), 0.89 (s, 3H), 0.07 (s, 3H), 0.06 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 140.63, 138.50, 126.06, 115.91, 81.76, 70.47, 61.84, 59.31, 57.59, 53.59, 43.76, 42.48, 26.05, 19.27, 18.31, 16.14, -3.97, -4.88 ppm; IR (neat) 2958, 2929, 2857, 2886, 1462, 1374, 1253, 1048, 1022, 836, 774 cm-1; HRMS (ESI) m/z Calcd for C20H36O3SiNa [M+Na]+ 375.2326, found 375.2337.
Synthesis of compound 23
To a solution of compound 22 (60 mg, 0.17 mmol) in DCM (9 mL) was added DMP (144 mg, 0.34 mmol) and NaHCO3 (71 mg, 0.85 mmol). The reaction was stirred at rt for 3 h, and then quenched with saturated NaHCO3 (10 mL), extracted with DCM (20 mL x 2). The combined organic phase was washed with NaHCO3 (20 mL) and brine (20 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 8:1) to afford 23 (53 mg, 88%) as a white solid. mp 108.5-109.7 °C. 1H NMR (400 MHz, C6D6) δ = 9.70 (d, J = 5.3 Hz, 1H), 6.18 (td, J = 10.1, 17.0 Hz, 1H), 5.39 (dd, J = 3.9, 9.4 Hz, 1H), 5.25(d, J = 9.4 Hz, 1H), 5.06 (dd, J = 2.4, 10.2 Hz, 1H), 5.02 (dd, J = 2.4, 17.1 Hz, 1H), 3.63 (d, J = 3.8 Hz, 1H), 2.69 (d, J = 10.0 Hz, 1H), 2.25 (d, J = 5.3 Hz, 1H), 1.07 (s, 1H), 0.96 (s, 12H), 0.89 (s,
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3H), 0.86 (s, 3H), 0.01 (s, 3H), 0.00 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 201.08, 138.66, 137.20, 127.87, 116.59, 82.76, 70.05, 69.84, 58.40, 53.80, 44.50, 26.38, 25.97, 18.69, 18.24, 15.91, -4.06, -4.99 ppm; IR (neat) 2958, 2929, 2855, 1710, 1374, 1251, 1055, 881,772 cm-1; HRMS (ESI) m/z Calcd for C20H34O3SiNa [M+Na]+ 373.2169, found 373.2193.
Synthesis of compound 24
To a stirred solution of compound 23 (25 mg, 0.071 mmol) in THF (5 mL) at 0 °C was added vinyl magnesium bromide (0.18 mL, 1M; freshly prepared following typical method) dropwise during 5 min. The reaction was stirred for 3 h at 0 °C under argon atmosphere, and then quenched with saturated NH4Cl (5 mL), extracted with EA (10 mL x 2). The combined organic phase was washed with saturated NaHCO3 (10 mL) and brine (10 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 10:1) to afford 24 (13 mg, 48%) as a white semi-solid. 1H NMR (400 MHz, C6D6) δ = 6.31 (td, J = 10.1, 17.0 Hz, 1H), 6.14-6.05 (m, 1H), 5.50 (s, 2H), 5.20-5.11 (m, 3H), 5.00 (td, J = 1.5, 10.4 Hz, 1H), 4.27-4.23 (m, 1H), 3.80 (d, J = 1.8 Hz, 1H), 2.96 (d, J = 8.2 Hz, 1H), 2.75 (d, J = 10.1 Hz, 1H), 2.22 (s, 1H), 1.62 (d, J = 3.3 Hz, 1H), 1.23 (s, 3H), 1.13 (s, 3H), 1.07 (s, 3H), 1.00 (s, 9H), 0.07 (s, 6H) ppm; 13C NMR (100 MHz, C6D6) δ = 143.20, 141.50, 138.74, 125.95, 84.35, 74.19, 70.44, 62.27, 58.11, 53.90, 44.91, 30.09, 27.20, 26.05, 25.98, 20.25, 18.31, 16.28, -3.96, -4.86 ppm; IR (neat) 2956, 2929, 2857, 1636, 1462, 1256, 1050, 836, 773 cm-1; HRMS (ESI) m/z Calcd for C22H38O3SiNa [M+Na]+ 401.2482, found 401.2492.
Synthesis of compound 25
To a stirred mixture of Pd(OAc)2 (1 mg, 0.005 mmol) and CuCl2 (17 mg, 0.13 mmol) in THF (0.5 mL) was added 1,1,3,3-tetramethylthiourea (TMTU) (0.7 mg, 0.005 mmol) at rt, and the formed mixture was stirred for 30 min under argon atmosphere. To this solution was added propene oxide (PO) (0.018 mL, 0.25 mmol) and NH4OAc (4 mg, 0.005 mmol), and the mixture was purged with CO, followed by dropwise addition of enediol 24 (19 mg, 0.05 mmol) in THF (0.1 mL) during 2 min, and the reaction was stirred at 50 °C under CO atmosphere for 12 h. After being cooled to rt, the reaction mixture was diluted with EA (20 mL), filtered through Celite. The filtrate was washed with saturated NH4Cl (10 mL) and brine (10 mL), dried over Na2SO4,
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and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 10:1-5:1) to afford 25 (16 mg, 78%) as a white semi-solid. 1H NMR (400 MHz, C6D6) δ = 6.22 (td, J = 10.0, 17.1 Hz, 1H), 5.53 (dd, J = 4.0, 9.5 Hz, 1H), 5.40 (d, J = 9.5 Hz, 1H), 5.22 (dd, J = 2.2, 17.1 Hz, 1H), 5.08 (dd, J = 2.4, 10.0 Hz, 1H), 3.90 (dd, J = 3.0, 6.6 Hz, 1H), 3.78 (d, J = 3.9 Hz, 1H), 3.65 (dd, J = 3.2, 4.4 Hz, 1H), 2.62 (d, J = 10.1 Hz, 1H), 2.28 (d, J = 17.6 Hz, 1H), 1.74 (dd, J = 4.5, 17.6 Hz, 1H), 1.59 (d, J = 6.6 Hz, 1H), 1.30 (s, 3H), 1.26 (s, 3H), 0.97 (s, 9H), 0.87 (s, 3H), 0.05 (s, 3H), 0.04 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 173.87, 139.66, 137.14, 126.86, 116.86, 94.71, 85.29, 78.10, 70.09, 62.78, 57.78, 51.87, 44.98, 34.51, 25.98, 20.64, 19.89, 18.29, 16.16, -3.98, -4.93 ppm; IR (neat) 2957, 2928, 2857, 1783, 1635, 1258, 1059, 774 cm-1; HRMS (ESI) m/z Calcd for C23H36O4SiNa [M+Na]+ 427.2275, found 427.2271.
Synthesis of compound 26 and 27
OTBS
OO
H
O
H
H
OTBS
OO
H
O
H
H
2) MsCl, Et3N, DMAPDCM, 35 oC, 40 h (A)/RT , 20 h (B)
+
OTBS
OO
H
O
H
H1) CH3CHO, LDA,THF, -78 oC, 3 h
25 26 27
To a solution of compound 25 (10 mg, 0.025 mmol) in THF (5 mL) was added LDA (0.15 mL, 1 M in THF, 0.15 mmol, freshly prepared following typical method) at -78 °C. The resultant mixture was stirred at the same temperature for 20 min, and acetaldehyde (10 μL, 0.17 mmol) was added. The reaction was stirred at -78 °C for 3 h, and then quenched with saturated NH4Cl (5 mL), extracted with EA (10 mL x 2). The combined organic phase was washed with saturated NaHCO3 (10 mL) and brine (10 mL), dried over Na2SO4, and evaporated to give a residue, which was subjected to the next process without further purification. Procedure A: To a solution of the above crude product in DCM (5 mL) was added Et3N (60 μL, 0.43 mmol), DMAP (1 mg) and MsCl (10 μL, 0.12 mmol). The resultant mixture was stirred at 35 °C for 40 h, and then quenched with saturated NH4Cl (5 mL), extracted with DCM (10 mL x 2). The combined organic phase was washed with saturated NaHCO3 (5 mL) and brine (5 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 8:1) to afford 26 (2.7 mg, 25% two steps) and 27 (6.5 mg, 61% two steps), both as a white semi-solid. Procedure B: To a solution of the above crude product in DCM (0.5 mL) was added Et3N (60 μL, 0.43 mmol), DMAP (1 mg) and MsCl (10 μL, 0.12 mmol). The resultant mixture was stirred at rt for 20 h, and then quenched with saturated NH4Cl (5 mL), extracted with DCM (10 mL x 2). The combined organic phase was washed with saturated NaHCO3 (5 mL) and brine (5 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 8:1) to afford 26 (5.5 mg, 52% two steps) and 27 (3.2 mg, 30% two steps).
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Compound 26: 1H NMR (400 MHz, C6D6) δ = 6.23 (td, J = 10.1, 17.1 Hz, 1H), 5.96 (q, J = 7.2 Hz, 1H), 5.54 (dd, J = 3.9, 9.5 Hz, 1H), 5.42 (d, J = 9.5 Hz, 1H), 5.19 (dd, J = 2.1, 17.0 Hz, 1H), 5.06 (dd, J = 2.3, 10.1 Hz, 1H), 4.14 (d, J = 3.2 Hz, 1H), 4.06 (dd, J = 3.4, 6.8 Hz, 1H), 3.80 (d, J = 3.8 Hz, 1H), 2.71 (d, J = 10.1 Hz, 1H), 1.97 (d, J = 7.3 Hz, 3H), 1.71 (d, J = 6.8 Hz, 1H), 1.36 (s, 3H), 1.30 (s, 3H), 0.97 (s, 3H), 0.95 (s, 9H), 0.05 (s, 3H), 0.02 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 167.84, 142.69, 139.78, 137.17, 127.16, 126.78, 116.80, 95.33, 83.55, 81.26, 70.14, 62.91, 57.84, 52.01, 45.16, 25.98, 21.09, 20.09, 18.28, 16.25, 14.14, -3.99, -4.93 ppm; IR (neat) 2957, 2929, 2857, 1761, 1686, 1258, 1130, 1117, 1053, 869, 837 cm-1; HRMS (ESI) m/z Calcd for C25H38O4SiNa [M+Na]+ 453.2432, found 453.2430. Compound 27: 1H NMR (400 MHz, C6D6) δ = 6.72 (dq, J = 0.9, 7.2 Hz, 1H), 6.22 (td, J = 10.0, 17.1 Hz, 1H), 5.54 (dd, J = 4.0, 9.5 Hz, 1H), 5.43 (d, J = 9.4 Hz, 1H), 5.16 (dd, J = 2.2, 17.0 Hz, 1H), 5.05 (dd, J = 2.4, 10.0 Hz, 1H), 4.39 (d, J = 3.0 Hz, 1H), 4.08 (dd, J = 3.7, 7.1 Hz, 1H), 3.79 (d, J = 3.9 Hz, 1H), 2.64 (d, J = 10.2 Hz, 1H), 1.75 (d, J = 7.1 Hz, 1H), 1.41 (d, J = 7.2 Hz, 3H), 1.38 (s, 3H), 1.26 (s, 3H), 0.96 (s, 3H), 0.95 (s, 9H), 0.05 (s, 3H), 0.02 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 168.66, 139.78, 139.74, 137.09, 128.71, 126.77, 116.83, 95.79, 84.02, 76.69, 70.08, 62.75, 57.90, 51.99, 45.18, 25.97, 21.23, 20.18, 18.27, 16.29, 15.39, -4.01, -4.95 ppm; IR (neat) 2957, 2929, 2857, 1766, 1693, 1056, 773 cm-1; HRMS (ESI) m/z Calcd for C25H38O4SiNa [M+Na]+ 453.2432, found 453.2430.
Synthesis of compound 26a
To a solution of compound 26 (5 mg, 0.012 mmol) in CH3CN (1 mL) was added aqueous HF (aq. 40%, 0.2 mL). The reaction was stirred at rt for 20 h, and then quenched with saturated NaHCO3 (2 mL), extracted with EA (5 mL x 2). The combined organic phase was washed with brine (5 mL x 2), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 3:1) to afford 26a (3.3 mg, 90%) as a white semi-solid. 1H NMR (400 MHz, C6D6) δ = 5.97-5.82 (m, 2H), 5.59 (dd, J = 4.0, 9.5 Hz, 1H), 5.35 (d, J = 9.4 Hz, 1H), 5.12 (dd, J = 1.4, 17.1 Hz, 1H), 4.96 (dd, J = 2.0, 10.3 Hz, 1H), 4.07 (d, J = 3.3 Hz, 1H), 4.00 (dd, J = 3.4, 6.8 Hz, 1H), 3.58-3.55 (m, 1H), 2.66 (d, J = 9.5 Hz, 1H), 1.98 (d, J = 7.3 Hz, 3H), 1.64 (d, J = 6.7 Hz, 1H), 1.28 (s, 3H), 1.26 (s, 3H), 1.15 (d, J = 8.3 Hz, 1H), 0.84 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 167.82, 142.68, 139.74, 135.62, 127.37, 127.14, 119.13, 95.30, 83.53, 81.15, 69.90, 62.74, 56.30, 51.96, 45.01, 20.85, 19.98, 15.43, 14.13 ppm; IR (neat) 2961, 2925, 1755, 1684, 1374, 1215, 1131, 1031, 1011, 965 cm-1; HRMS (ESI) m/z Calcd for C19H24O4Na [M+Na]+ 339.1567, found 339.1568.
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Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Synthesis of pallambin C (1)
To a solution of compound 26a (3 mg, 0.0095 mmol) in DCM (0.5 mL) was added DMP (8 mg, 0.019 mmol) and NaHCO3 (4 mg, 0.048 mmol). The reaction was stirred at rt for 1 h, and then quenched with saturated Na2S2O3 (2 mL), extracted with DCM (5 mL x 2). The combined organic phase was washed with aqueous NaHCO3 (5 mL) and brine (5 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 3:1) to afford 1 (2.8 mg, 95%) as a colorless oil. 1H NMR (400 MHz, CDCl3) δ = 6.71-6.66 (m, 2H), 5.89 (d, J = 9.6 Hz, 1H), 5.54 (td, J = 9.8, 16.9 Hz, 1H), 5.22-5.15 (m, 2H), 4.88 (dd, J = 3.2, 6.7 Hz, 1H), 4.84 (d, J = 3.2 Hz, 1H), 2.83 (dd, J = 1.6, 9.5 Hz, 1H), 2.53 (d, J = 6.7 Hz, 1H), 2.25 (d, J = 7.3 Hz, 3H), 1.42 (s, 3H), 1.14 (s, 3H), 1.04 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ = 201.56, 168.38, 157.11, 144.82, 132.39, 127.01, 126.10, 121.78, 94.17, 83.13, 82.34, 63.98, 62.79, 60.83, 47.02, 22.43, 19.68, 14.60, 12.88 ppm; IR (neat) 2967, 2929, 1759, 1681, 1375, 1118, 916 cm-1; HRMS (ESI) m/z Calcd for C19H23O4 [M+H]+ 315.1591, found 315.1606.
Synthesis of compound 27a
To a solution of compound 27 (5 mg, 0.012 mmol) in CH3CN (1 mL) was added aqueous HF (aq. 40%, 0.2 mL). The reaction was stirred at rt for 20 h, and then quenched with saturated NaHCO3 (2 mL), extracted with EA (5 mL x 2). The combined organic phase was washed with brine (5 mL x 2), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 3:1) to afford 27a (3.3 mg, 90%) as a white semi-solid. 1H NMR (400 MHz, C6D6) δ = 6.72 (q, J = 7.2 Hz, 1H), 5.86 (td, J = 9.9, 17.2 Hz, 1H), 5.59 (dd, J = 4.0, 9.4 Hz, 1H), 5.35 (d, J = 9.4 Hz, 1H), 5.09 (dd, J = 1.4, 17.2 Hz, 1H), 4.95 (dd, J = 1.9, 10.2 Hz, 1H), 4.32 (d, J = 3.1 Hz, 1H), 4.02 (dd, J = 3.6, 7.0 Hz, 1H), 3.55-3.52 (m, 1H), 2.61 (d, J = 9.4 Hz, 1H), 1.67 (d, J = 7.0 Hz, 1H), 1.39 (d, J = 7.2 Hz, 3H), 1.31 (s, 3H), 1.23 (s, 3H), 1.15 (d, J = 8.3 Hz, 1H), 0.83 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 168.64, 139.75, 135.56, 128.68, 127.33, 119.11, 95.78, 84.00, 76.58, 69.84, 62.57, 56.37, 51.94, 45.02, 20.97, 20.07, 15.48, 15.40 ppm; IR (neat) 2956, 2927, 1756, 1693, 1375, 1217, 1143, 1074, 1031, 738 cm-1; HRMS (ESI) m/z Calcd
22
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
for C19H24O4Na [M+Na]+ 339.1567, found 339.1568.
Synthesis of pallambin D (2)
To a solution of compound 27a (3 mg, 0.0095 mmol) in DCM (0.5 mL) was added DMP (8 mg, 0.019 mmol) and (4 mg, 0.048 mmol). The reaction was stirred at rt for 2 h, and then quenched with saturated Na2S2O3 (2 mL), extracted with DCM (5 mL x 2). The combined organic phase was washed with aqueous NaHCO3 (5 mL) and brine (5 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 3:1) to afford 2 (2.6 mg, 89%) as a white solid. mp 184.5-185.7 °C (lit.[1] mp 191 °C). 1H NMR (400 MHz, CDCl3) δ = 7.00 (q, J = 7.3 Hz, 1H), 6.69 (dd, J = 1.9, 9.5 Hz, 1H), 5.89 (d, J = 9.6 Hz, 1H), 5.53 (td, J = 9.8, 16.9 Hz, 1H), 5.20-5.15 (m, 2H), 5.09 (d, J = 3.2 Hz, 1H), 4.90 (dd, J = 3.6, 7.0 Hz, 1H), 2.76 (dd, J = 1.8, 9.4 Hz, 1H), 2.56 (d, J = 7.0 Hz, 1H), 2.03 (d, J = 7.2 Hz, 3H), 1.42 (s, 3H), 1.16 (s, 3H), 1.01 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ = 201.61, 169.53, 157.12, 141.89, 132.37, 127.68, 126.97, 121.73, 94.51, 83.80, 77.76, 64.03, 62.79, 60.62, 47.03, 22.50, 19.78, 16.18, 12.84 ppm; IR (neat) 2967, 2931, 1764, 1682, 1376, 1209, 1121, 1072, 973 cm-1; HRMS (ESI) m/z Calcd for C19H23O4 [M+H]+ 315.1591, found 315.1594. 1 M. Toyota, T. Sato, Y. Asakawa, Chem. Pharm. Bull. 1998, 46, 178 – 180.
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Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Spectral comparison between natural and synthetic
Pallambin C (1):
H Natural (600M, CDCl3,
solvent signal 7.28, δ ppm)Synthetic (400M, CDCl3, solvent signal 7.26, δ ppm)
1 6.69 (m) 6.68 (m) 2 5.89 (d, 9.6) 5.89 (d, 9.6) 5 2.84 (dd, 9.9, 2.0) 2.83 (dd, 9.5, 1.6) 6 5.54 (dt, 17.0, 9.9) 5.54 (dt, 16.9, 9.8) 7 5.19 (2H, m) 5.18 (2H, m) 9 2.54 (d, 6.7) 2.53 (d, 6.7) 11 4.89 (dd, 6.8, 3.3) 4.88 (dd, 6.7, 3.2) 12 4.85 (d, 3.3) 4.84 (d, 3.2) 14 6.69 (1H, m) 6.67 (1H, m) 15 2.26 (3H, d, 7.3) 2.25 (3H, d, 7.3) 17 1.15 (3H, S) 1.14 (3H, S) 18 1.04 (3H, S) 1.04 (3H, S) 19 1.42 (3H, S) 1.42 (3H, S)
C Natural (150M, CDCl3, solvent signal 77.02, δ
ppm)
Synthetic (100M, CDCl3, solvent signal 77.16, δ
ppm) 1 156.9 157.1 2 126.8 127.0 3 201.3 201.6 4 62.6 62.8 5 63.8 64.0 6 132.2 132.4 7 121.5 121.8 8 94.0 94.2 9 60.6 60.8 10 46.8 47.0 11 82.9 83.1
24
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
12 82.1 82.3 13 125.9 126.1 14 144.6 144.8 15 14.4 14.6 16 168.1 168.4 17 22.2 22.4 18 12.7 12.9 19 19.5 19.7
Pallambin D (2):
O
OO
H
O
H
H
12
3
45
67
1789
1019 18
14
1211
13
15
16
H Natural (600M, CDCl3,
solvent signal 7.28, δ ppm)Synthetic (400M, CDCl3, solvent signal 7.26, δ ppm)
1 6.70 (dd, 9.6, 2.1) 6.69 (dd, 9.5, 1.9) 2 5.91 (d, 9.6) 5.89 (d, 9.6) 5 2.78 (dd, 9.9, 2.0) 2.76 (dd, 9.4, 1.8) 6 5.55 (dt, 16.9, 9.9) 5.53 (dt, 16.9, 9.8) 7 5.19 (2H, m) 5.17 (2H, m) 9 2.58 (d, 7.0) 2.56 (d, 7.0) 11 4.92 (dd, 7.0, 3.6) 4.90 (dd, 7.0, 3.6) 12 5.11 (dd, 3.5, 0.8) 5.09 (d, 3.2) 14 7.07 (qd, 7.2, 0.8) 7.00 (q, 7.3) 15 2.06 (3H, d, 7.2) 2.03 (3H, d, 7.2) 17 1.18 (3H, S) 1.16 (3H, S) 18 1.03 (3H, S) 1.01 (3H, S) 19 1.44 (3H, S) 1.42 (3H, S)
C Natural (150M, CDCl3, solvent signal 77.00, δ
ppm)
Synthetic (100M, CDCl3, solvent signal 77.16, δ
ppm) 1 157.0 157.1 2 126.8 127.0 3 201.3 201.6 4 62.7 62.8 5 63.9 64.0 6 132.2 132.4
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Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7 121.5 121.7 8 94.4 94.5 9 60.3 60.6 10 46.7 47.0 11 83.6 83.8 12 77.6 77.8 13 127.5 127.7 14 141.7 141.9 15 16.0 16.2 16 169.3 169.5 17 22.3 22.5 18 12.7 12.8 19 19.6 19.8
26
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
Basic crystal data for compounds 2, 10, 11, 16 and 22 CCDC 879025 (2), CCDC 879026 (10), CCDC 879027 (11), CCDC 879028 (16) and CCDC 879029 (22) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. Chem. Commun. Deposition Number(s) 879025 879026 879027 879028 879029 CIF files for 5 structures are attached to this message. CCDC No Acell Bcell Ccell Space Gp. 879025 7.3712 8.0916 13.8262 P-1 879026 14.4194 14.4194 6.0541 P32 879027 8.3310 8.7830 13.7240 P-1 879028 14.7240 6.7900 22.3940 P21/n 879029 11.6292 7.7435 12.2967 P21
ORTEP diagram of compound 2. Thermal ellipsoids were plotted at 30 % probability level. Hydrogen atoms are omitted for clarity.
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Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
ORTEP diagram of compound 10. Thermal ellipsoids were plotted at 30 % probability level. Hydrogen atoms are omitted for clarity.
ORTEP diagram of compound 11. Thermal ellipsoids were plotted at 30 % probability level. Hydrogen atoms are omitted for clarity.
28
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
ORTEP diagram of compound 16. Thermal ellipsoids were plotted at 30 % probability level. Hydrogen atoms are omitted for clarity.
ORTEP diagram of compound 22. Thermal ellipsoids were plotted at 30 % probability level. Hydrogen atoms are omitted for clarity.
29
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
natu
ral
600 M
Hz in C
DC
L3
ppm
(t1)
1.0
2.0
3.0
4.0
5.0
6.0
synth
etic
400 M
Hz
in C
DC
l3
30
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
150M
Hz
in C
DC
l3
natu
ral
ppm
(t1)
5010
015
020
0
synth
etic
100 M
Hz
in C
DC
l3
31
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
600 M
Hz
in C
DC
l3
natu
ral
ppm
(f1)
1.0
2.0
3.0
4.0
5.0
6.0
7.0
synth
etic
400 M
Hz
in C
DC
l3
32
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
natu
ral
150 M
Hz
in C
DC
l3
ppm
(t1)
5010
015
020
0
synth
etic
100 M
Hz
in C
DC
l3
33
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
1.0677
1.2274
1.2388
1.2514
1.2618
1.2725
1.2847
1.2955
1.3062
1.3178
1.3280
1.3383
1.4292
1.4404
1.4567
1.4764
1.5376
1.5474
1.5690
1.5783
1.5985
1.6031
1.6091
1.6272
1.7471
1.7519
1.7582
1.7640
1.7767
1.7817
1.8079
1.8199
1.8336
1.8469
1.8591
1.9326
1.9379
1.9427
1.9671
1.9771
1.9904
2.0075
2.0970
2.1029
2.1088
2.1317
2.1372
2.1432
2.1663
2.1716
2.1778
3.2388
3.2496
3.2619
3.2670
3.2785
3.2890
4.1750
4.1844
5.4097
7.2599
3.152
1.164
4.140
1.100
3.198
2.148
1.117
1.028
1.031
1.000
NAME XS-1-7-A1EXPNO 1PROCNO 1Date_ 20110919Time 18.50INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 6DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 101DW 60.800 usecDE 6.50 usecTE 298.9 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.00 usecPL1 -1.00 dBPL1W 13.56617069 WSFO1 400.1924713 MHzSI 32768SF 400.1900141 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-7-A1EXPNO 2PROCNO 1Date_ 20110919Time 18.57INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 176DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 299.3 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.90 usecPL1 -2.00 dBPL1W 55.33689499 WSFO1 100.6379183 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -1.00 dBPL12 15.16 dBPL13 18.62 dBPL2W 13.56617069 WPL12W 0.32844096 WPL13W 0.14806664 WSFO2 400.1916008 MHzSI 32768SF 100.6278427 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.916
24.709
28.998
30.851
31.464
33.636
40.762
67.787
76.843
77.160
77.478
79.217
126.055
144.917
Bruker Advance III 400
34
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
1.1483
1.1716
1.1822
1.1924
1.2059
1.2159
1.2257
1.2393
1.2495
1.2594
1.3054
1.3178
1.3461
1.3804
1.5357
1.5643
1.5701
1.5818
1.5974
1.7926
1.8109
1.8211
1.9617
1.9851
1.9961
2.0235
2.0295
2.0422
2.1461
2.1516
2.1748
2.1800
2.1859
2.2092
2.9562
2.9666
2.9851
2.9955
3.9360
3.9468
3.9516
3.9654
4.4111
4.4408
4.5440
4.5739
4.6017
4.6314
4.6459
4.6756
5.4924
7.2597
7.2741
7.2852
7.2900
7.2945
7.3245
7.3384
7.3486
7.3605
7.3809
3.097
1.039
1.263
2.336
1.288
4.186
1.153
1.014
1.008
1.063
1.100
1.157
1.031
1.000
10.370
NAME XS-1-5-A1EXPNO 2PROCNO 1Date_ 20110923Time 17.03INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 5DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 50.8DW 60.800 usecDE 6.50 usecTE 299.4 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.00 usecPL1 -1.00 dBPL1W 13.56617069 WSFO1 400.1924713 MHzSI 32768SF 400.1900141 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-5-A1EXPNO 3PROCNO 1Date_ 20110923Time 17.08INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 79DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 299.8 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.90 usecPL1 -2.00 dBPL1W 55.33689499 WSFO1 100.6379183 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -1.00 dBPL12 15.16 dBPL13 18.62 dBPL2W 13.56617069 WPL12W 0.32844096 WPL13W 0.14806664 WSFO2 400.1916008 MHzSI 32768SF 100.6278456 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
17.994
24.633
25.349
26.744
31.780
34.067
41.126
70.049
71.437
74.484
76.843
77.160
77.478
86.455
123.386
127.448
127.536
127.561
127.812
128.350
128.453
139.140
139.396
145.593
Bruker Advance III 400
35
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
0.9381
0.9741
1.1936
1.2443
1.2505
1.2800
1.3135
1.3195
1.4330
1.4412
1.4570
1.4658
1.4750
1.4905
1.4997
1.5103
1.5264
1.5347
1.5626
1.5716
1.5980
1.6056
1.6202
1.6393
1.6478
1.7346
1.7450
1.7577
1.8912
1.9009
1.9113
1.9338
1.9434
1.9780
1.9900
2.0123
2.0227
2.0439
3.0445
3.3278
3.3390
3.3546
3.3654
3.7015
3.7217
3.7252
3.7446
4.4217
4.4513
4.6327
4.6604
7.2591
7.2670
7.2782
7.2890
7.2997
7.3253
7.3358
7.3622
7.3683
7.3757
1.014
3.009
1.082
1.119
3.084
1.028
1.065
2.040
0.988
1.006
1.000
1.024
2.070
1.012
10.063
NAME XS-1-9-A1EXPNO 1PROCNO 1Date_ 20110924Time 15.14INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 4DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 36DW 60.800 usecDE 6.50 usecTE 298.7 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.00 usecPL1 -1.00 dBPL1W 13.56617069 WSFO1 400.1924713 MHzSI 32768SF 400.1900144 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-9-A1EXPNO 2PROCNO 1Date_ 20110924Time 15.19INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 56DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 299.2 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.90 usecPL1 -2.00 dBPL1W 55.33689499 WSFO1 100.6379183 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -1.00 dBPL12 15.16 dBPL13 18.62 dBPL2W 13.56617069 WPL12W 0.32844096 WPL13W 0.14806664 WSFO2 400.1916008 MHzSI 32768SF 100.6278471 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.251
20.744
24.071
26.476
27.556
29.139
38.883
61.533
66.622
71.320
71.677
72.701
76.845
77.162
77.480
83.692
127.461
127.528
127.863
128.351
128.578
138.331
139.313
Bruker Advance III 400
36
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
1.0630
1.0933
1.4175
1.4301
1.4503
1.4624
1.4810
1.4929
1.5122
1.5247
1.6033
1.6214
1.6283
1.6424
1.6500
1.6620
1.6687
1.6792
1.6924
1.7092
1.7145
1.7264
1.7378
1.7445
1.7597
1.7720
1.7940
1.8112
1.8215
1.8626
1.8802
1.8944
1.9628
1.9812
1.9984
2.0149
2.0334
2.0482
2.0558
2.0610
2.0819
2.0950
2.1155
2.1287
3.5375
3.5488
3.5663
3.5776
4.0372
4.0504
4.0642
4.0777
4.0912
4.4243
4.4538
4.4774
4.5071
4.5399
4.5696
4.5906
4.6200
5.2948
7.2600
7.2711
7.2805
7.2883
7.3263
7.3374
7.3576
7.3725
0.942
3.208
3.159
1.088
7.950
2.114
1.000
1.045
1.014
1.011
1.041
0.973
10.559
NAME XS-1-16-A1EXPNO 1PROCNO 1Date_ 20110926Time 15.13INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 4DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 40.3DW 60.800 usecDE 6.50 usecTE 298.8 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.00 usecPL1 -1.00 dBPL1W 13.56617069 WSFO1 400.1924713 MHzSI 32768SF 400.1900138 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-16-A1EXPNO 2PROCNO 1Date_ 20110926Time 15.17INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 64DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 181DW 20.800 usecDE 6.50 usecTE 299.3 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.90 usecPL1 -2.00 dBPL1W 55.33689499 WSFO1 100.6379183 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -1.00 dBPL12 15.16 dBPL13 18.62 dBPL2W 13.56617069 WPL12W 0.32844096 WPL13W 0.14806664 WSFO2 400.1916008 MHzSI 32768SF 100.6278464 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
10.328
15.259
19.052
23.524
26.259
30.354
32.806
42.417
45.709
69.958
71.887
76.596
76.842
77.160
77.478
78.907
82.122
127.321
127.451
127.470
127.549
128.310
128.452
139.318
139.716
Bruker Advance III 400
37
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
4.4858
4.5158
4.5208
4.5510
1.1136
1.1229
1.1473
1.1571
1.1811
1.1908
1.2524
1.2711
1.2820
1.6794
1.6942
1.7065
1.7243
1.7356
1.7533
1.7656
1.7837
1.7956
1.8050
1.8178
1.8282
1.8375
1.8500
1.8595
1.8872
1.9142
1.9219
1.9565
1.9655
1.9727
1.9973
2.0968
2.1074
2.1364
2.1419
2.1644
2.1737
2.1896
2.1979
2.2351
2.2479
2.8389
2.8565
2.8732
2.8899
2.9074
3.1666
3.1744
3.1970
3.2048
3.4509
3.4633
3.4784
3.4923
3.5043
4.6358
4.6656
4.7302
4.7599
5.4223
7.2603
7.3162
7.3327
7.3488
7.3852
7.4037
7.4189
1.171
2.981
2.979
4.336
3.100
1.008
1.004
1.009
0.988
1.034
1.043
1.024
1.000
10.226
NAME XS-1-17-A1EXPNO 2PROCNO 1Date_ 20110922Time 13.16INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 8DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 12.7DW 60.800 usecDE 6.50 usecTE 299.4 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.00 usecPL1 -1.00 dBPL1W 13.56617069 WSFO1 400.1924713 MHzSI 32768SF 400.1900133 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-17-A1EXPNO 3PROCNO 1Date_ 20110922Time 13.21INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 60DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 228DW 20.800 usecDE 6.50 usecTE 299.8 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.90 usecPL1 -2.00 dBPL1W 55.33689499 WSFO1 100.6379183 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -1.00 dBPL12 15.16 dBPL13 18.62 dBPL2W 13.56617069 WPL12W 0.32844096 WPL13W 0.14806664 WSFO2 400.1916008 MHzSI 32768SF 100.6278596 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
16.549
20.639
22.721
23.185
25.168
36.525
39.288
41.551
69.658
71.195
76.841
77.160
77.478
79.908
85.611
122.337
127.340
127.397
127.471
128.276
128.387
139.194
139.416
145.665
Bruker Advance III 400
38
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
3.7915
3.8533
1.0063
1.0204
1.0388
1.0636
1.0749
1.2283
1.2394
1.2619
1.2956
1.3212
1.3321
1.4709
1.5007
1.5303
1.5394
1.5638
1.5739
1.6877
1.7160
1.7242
1.7349
1.7440
1.9062
1.9139
1.9255
1.9388
1.9467
2.0044
2.0125
2.0305
2.0379
2.0875
2.0957
2.1071
2.1186
2.1266
2.6529
2.6650
2.6827
2.6947
2.7128
2.8677
2.8777
2.8963
2.9063
3.3692
3.3838
3.4012
3.4087
3.4223
3.8020
3.8171
3.8273
3.8427
4.3997
4.4293
4.4611
4.4909
4.5999
4.6185
4.6293
4.6481
7.2600
7.2793
7.2954
7.3315
7.3481
7.3660
7.3824
3.115
3.179
1.989
1.123
2.042
2.274
1.008
0.987
0.985
1.007
0.999
1.003
1.000
0.968
0.982
2.048
10.102
NAME XS-1-20-A1EXPNO 2PROCNO 1Date_ 20110927Time 12.30INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 4DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 28.5DW 60.800 usecDE 6.50 usecTE 299.3 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.00 usecPL1 -1.00 dBPL1W 13.56617069 WSFO1 400.1924713 MHzSI 32768SF 400.1900141 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-20-A1EXPNO 3PROCNO 1Date_ 20110927Time 21.14INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 41DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 181DW 20.800 usecDE 6.50 usecTE 299.2 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.90 usecPL1 -2.00 dBPL1W 55.33689499 WSFO1 100.6379183 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -1.00 dBPL12 15.16 dBPL13 18.62 dBPL2W 13.56617069 WPL12W 0.32844096 WPL13W 0.14806664 WSFO2 400.1916008 MHzSI 32768SF 100.6278508 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
9.142
14.715
23.274
24.971
30.284
34.228
37.008
39.426
51.453
66.960
69.608
71.493
76.845
77.163
77.481
80.592
86.884
127.461
127.575
128.330
128.437
139.170
139.252
Bruker Advance III 400
39
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
1.2516
1.2756
1.3023
1.3138
1.3244
1.3426
1.3533
1.5096
1.5201
1.5438
1.5494
1.5533
1.5728
1.5828
1.6070
1.6178
1.6310
1.6593
1.6673
1.6918
1.6966
1.7194
1.7286
1.7395
1.7518
1.7609
1.9097
1.9171
1.9285
1.9428
1.9505
2.0262
2.0351
2.0538
2.0834
2.1635
2.1712
2.1828
2.1946
2.2023
2.2131
2.3994
2.4116
2.4293
2.4411
2.8771
2.8873
2.9059
2.9160
3.3608
3.3732
3.3864
3.4012
3.4137
4.3909
4.4204
4.4935
4.5233
4.5662
4.5987
4.6291
4.9763
4.9882
5.0039
5.0160
5.0317
5.0437
7.2603
7.2731
7.2773
7.2866
7.2933
7.2991
7.3065
7.3233
7.3404
7.3456
7.3616
3.094
3.001
0.892
2.153
1.090
2.008
1.095
1.066
3.013
1.081
1.023
1.000
1.008
0.986
0.978
1.035
0.947
1.020
10.333
NAME XS-1-21-A1EXPNO 1PROCNO 1Date_ 20110927Time 21.20INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 2DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 40.3DW 60.800 usecDE 6.50 usecTE 298.8 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.00 usecPL1 -1.00 dBPL1W 13.56617069 WSFO1 400.1924713 MHzSI 32768SF 400.1900138 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-21-A1EXPNO 2PROCNO 1Date_ 20110927Time 21.25INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 72DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 299.4 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.90 usecPL1 -2.00 dBPL1W 55.33689499 WSFO1 100.6379183 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -1.00 dBPL12 15.16 dBPL13 18.62 dBPL2W 13.56617069 WPL12W 0.32844096 WPL13W 0.14806664 WSFO2 400.1916008 MHzSI 32768SF 100.6278471 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
9.134
14.590
21.347
22.972
24.692
30.307
30.837
36.898
39.745
48.877
69.860
70.102
71.487
76.841
77.159
77.477
80.594
86.457
127.500
127.536
128.362
128.448
139.148
139.207
170.700
Bruker Advance III 400
40
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
0.8600
0.8786
0.9431
1.1021
1.1237
1.1349
1.1468
1.1785
1.3140
1.3260
1.3450
1.3552
1.3736
1.3846
1.4134
1.4490
1.5419
1.5525
1.5754
1.5856
1.6157
1.6304
1.6389
1.6524
1.6612
1.7029
1.7098
1.7222
1.7358
1.7430
1.8015
1.8094
1.8179
1.8344
1.8427
1.8505
2.0237
2.1107
2.1180
2.1301
2.1420
2.1488
2.2450
2.2573
2.2750
2.2868
3.1899
3.1992
3.2185
3.2273
3.6594
3.6747
3.6864
3.6969
3.7108
4.9400
4.9518
4.9678
4.9799
4.9956
5.0075
7.2601
3.014
3.049
1.172
4.012
1.292
2.041
1.085
1.095
3.017
1.099
1.033
1.023
1.039
1.000
NAME XS-1-2-A1EXPNO 1PROCNO 1Date_ 20110928Time 14.29INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 2DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 101DW 60.800 usecDE 6.50 usecTE 298.8 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.00 usecPL1 -1.00 dBPL1W 13.56617069 WSFO1 400.1924713 MHzSI 32768SF 400.1900138 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-2-A1EXPNO 2PROCNO 1Date_ 20110927Time 21.34INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 200DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 299.3 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.90 usecPL1 -2.00 dBPL1W 55.33689499 WSFO1 100.6379183 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -1.00 dBPL12 15.16 dBPL13 18.62 dBPL2W 13.56617069 WPL12W 0.32844096 WPL13W 0.14806664 WSFO2 400.1916008 MHzSI 32768SF 100.6278427 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
8.589
13.446
21.280
25.687
28.616
30.320
33.639
36.525
38.929
48.568
69.790
73.691
76.842
77.160
77.477
79.263
170.751
Bruker Advance III 400
41
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
1.0766
1.0935
1.1515
1.1709
1.3149
1.3965
1.6122
1.6164
1.6195
1.6247
1.6292
1.6386
1.6425
1.6484
1.6509
1.6555
1.6609
1.6743
1.6965
1.7758
1.7913
1.7984
1.8040
1.8110
1.8258
1.8888
1.9119
1.9245
1.9469
1.9594
1.9698
1.9769
1.9860
1.9936
2.0085
2.0127
2.0221
2.0303
2.0471
2.0526
2.0994
2.1061
2.1080
2.1138
2.1235
2.1352
2.1428
2.1572
2.1716
2.1859
2.3275
2.3337
2.3370
2.3404
2.3456
2.3581
2.3647
2.3719
2.3773
2.3804
2.3839
2.3923
2.3994
2.4128
2.4153
2.4266
2.4343
2.4435
2.4472
2.4542
2.4656
2.4736
2.5432
2.5597
2.5763
2.5885
2.5937
2.5996
2.6104
2.6155
2.6231
2.6269
2.6334
2.6500
2.6857
2.7042
2.7229
2.7380
2.7542
2.7746
2.7908
2.8111
2.8271
5.1701
5.1935
5.3219
5.3339
5.3493
5.3613
5.3770
5.3888
7.2600
0.849
1.934
0.854
1.929
1.298
6.441
6.193
0.301
0.699
NAME XS-1-6-A1EXPNO 2PROCNO 1Date_ 20111011Time 10.59INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zg30TD 65536SOLVENT CDCl3NS 2DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 71.8DW 60.800 usecDE 6.50 usecTE 294.2 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 7.10 usecPL1 -2.00 dBPL1W 13.17734718 WSFO1 400.1324710 MHzSI 32768SF 400.1300096 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-6-A1EXPNO 4PROCNO 1Date_ 20111012Time 11.03INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zgpg30TD 65536SOLVENT CDCl3NS 301DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 294.6 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 14.50 usecPL1 -4.00 dBPL1W 90.22689819 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -2.00 dBPL12 20.06 dBPL13 22.00 dBPL2W 13.17734718 WPL12W 0.08200268 WPL13W 0.05245997 WSFO2 400.1316005 MHzSI 32768SF 100.6127583 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
14.069
17.837
19.201
21.125
21.571
29.390
30.794
32.493
34.045
34.517
35.176
36.017
44.282
45.021
46.275
46.608
48.679
50.679
67.991
71.801
76.843
77.161
77.479
170.599
211.238
213.155
Bruker Advance III 400
42
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
0.8656
0.8844
1.1055
1.1229
1.1386
1.1658
1.4158
1.4230
1.4481
1.4562
1.5164
1.5236
1.5382
1.5510
1.5583
1.5858
1.5917
1.6179
1.6576
1.6920
1.7404
1.7739
1.8628
2.0375
2.0547
2.0659
2.0844
2.0955
2.1861
2.1996
2.2211
2.2276
2.2350
2.2409
2.2598
2.2653
2.2724
2.2784
2.3005
2.3171
2.3299
2.3483
2.6288
2.6456
2.6652
2.6819
2.7014
2.7180
3.3211
3.3262
3.3439
3.3484
3.3554
3.3608
3.3656
3.3731
3.3949
3.4132
3.4357
5.2396
5.2515
5.2674
5.2792
5.2950
5.3068
7.2602
3.073
6.017
2.922
5.140
2.916
1.070
3.091
1.005
4.034
1.000
NAME XS-1-10-A1EXPNO 1PROCNO 1Date_ 20111009Time 15.23INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 2DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 20.2DW 60.800 usecDE 6.50 usecTE 299.0 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.00 usecPL1 -1.00 dBPL1W 13.56617069 WSFO1 400.1924713 MHzSI 32768SF 400.1900136 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-10-A1EXPNO 2PROCNO 1Date_ 20111009Time 15.28INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 53DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 299.5 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.90 usecPL1 -2.00 dBPL1W 55.33689499 WSFO1 100.6379183 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -1.00 dBPL12 15.16 dBPL13 18.62 dBPL2W 13.56617069 WPL12W 0.32844096 WPL13W 0.14806664 WSFO2 400.1916008 MHzSI 32768SF 100.6278475 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
11.482
15.290
15.389
19.680
21.234
23.908
29.531
30.933
35.251
35.347
45.750
47.040
54.702
54.920
68.758
76.842
77.161
77.478
101.824
170.710
212.790
Bruker Advance III 400
43
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
2.5746
0.4361
0.9223
0.9352
0.9404
1.0303
1.0478
1.0654
1.0937
1.1113
1.1290
1.4745
1.4983
1.5067
1.5499
1.5575
1.5822
1.5914
1.6014
1.6115
1.6267
1.6346
1.7067
1.7425
1.9348
1.9479
1.9631
1.9779
1.9924
2.0060
2.1720
2.1832
2.2012
2.2122
2.5442
2.5575
3.1705
3.1930
3.2106
3.3497
3.3677
3.3852
3.3999
3.4176
3.4346
3.5796
5.8848
5.8915
5.8972
5.9043
7.1600
5.896
2.823
3.066
1.135
3.219
0.987
1.062
1.121
1.029
1.092
3.266
1.018
1.000
NAME XS-1-31-A1EXPNO 11PROCNO 1Date_ 20111101Time 16.36INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT C6D6NS 4DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 128DW 60.800 usecDE 6.50 usecTE 302.5 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.00 usecPL1 -1.00 dBPL1W 13.56617069 WSFO1 400.1924713 MHzSI 32768SF 400.1900016 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-31-A1EXPNO 14PROCNO 1Date_ 20111103Time 21.01INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT C6D6NS 6000DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 228DW 20.800 usecDE 6.50 usecTE 300.2 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.90 usecPL1 -2.00 dBPL1W 55.33689499 WSFO1 100.6379183 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -1.00 dBPL12 15.16 dBPL13 18.62 dBPL2W 13.56617069 WPL12W 0.32844096 WPL13W 0.14806664 WSFO2 400.1916008 MHzSI 32768SF 100.6278185 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
11.515
15.522
15.566
20.798
25.664
34.679
39.898
40.979
42.991
48.151
54.951
55.051
64.394
102.879
117.846
127.820
128.062
128.303
134.708
Bruker Advance III 400
44
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
0.9618
0.9800
1.0336
1.4933
1.5019
1.5145
1.5298
1.5358
1.5455
1.5497
1.5596
1.5691
1.5858
1.6090
1.6116
1.6191
1.6338
1.6445
1.6517
1.8089
1.8231
1.8480
1.8588
1.8872
1.8943
2.0856
2.0926
2.1076
2.1147
2.1286
2.1356
2.1506
2.1577
2.2591
2.2705
2.2950
2.3077
2.3116
2.3193
2.3236
2.6228
2.6370
2.6510
2.6657
2.6799
2.6940
3.7026
3.7177
3.7246
3.7303
3.7397
3.7454
3.7524
3.7675
3.8845
3.8934
3.8965
3.9063
3.9178
3.9339
3.9452
3.9556
3.9579
3.9673
4.4042
4.4327
4.6208
4.6493
6.1554
6.1625
6.1685
6.1756
7.2603
7.2699
7.2761
7.2852
7.2928
7.3024
7.3068
7.3136
7.3169
7.3302
7.3443
7.3470
7.3511
7.3615
7.3652
3.035
3.023
2.111
1.058
1.019
1.038
2.052
1.011
1.054
4.084
1.007
1.009
1.000
5.163
NAME XS-33-A1EXPNO 1PROCNO 1Date_ 20101004Time 17.02INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zg30TD 65536SOLVENT CDCl3NS 8DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 90.5DW 60.800 usecDE 6.50 usecTE 294.3 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 7.10 usecPL1 -2.00 dBPL1W 13.17734718 WSFO1 400.1324710 MHzSI 32768SF 400.1300051 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-33-A1EXPNO 2PROCNO 1Date_ 20101004Time 17.08INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zgpg30TD 65536SOLVENT CDCl3NS 200DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 294.6 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 14.50 usecPL1 -4.00 dBPL1W 90.22689819 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -2.00 dBPL12 18.80 dBPL13 18.80 dBPL2W 13.17734718 WPL12W 0.10960442 WPL13W 0.10960442 WSFO2 400.1316005 MHzSI 32768SF 100.6127561 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
12.006
20.717
27.615
36.147
37.401
40.199
42.337
47.579
64.232
64.483
71.024
71.358
76.841
77.159
77.476
111.574
117.249
127.767
127.863
128.490
134.053
138.536
Bruker Advance III 400
45
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
1.0062
1.0249
1.2716
1.4436
1.4526
1.4878
1.5145
1.5218
1.8876
1.9006
1.9240
1.9343
1.9604
1.9681
2.0163
2.0277
2.0445
2.0565
2.1539
2.1612
2.1750
2.1824
2.2012
2.2085
2.2224
2.2298
2.2921
2.2987
2.3089
2.3245
2.3317
2.3439
2.3609
2.3755
2.3794
2.3926
2.4056
2.4099
2.4241
2.8127
2.8268
2.8401
2.8600
2.8740
2.8874
3.6783
3.7252
3.7409
3.7463
3.7540
3.7618
3.7695
3.7748
3.7906
3.8713
3.8842
3.8928
3.9057
3.9286
3.9419
3.9554
3.9613
4.4346
4.4630
4.6568
4.6852
6.5835
6.5913
6.5950
6.6028
7.2604
7.2726
7.2847
7.2951
7.3061
7.3165
7.3380
7.3486
3.046
3.136
2.107
1.059
1.200
1.066
1.021
1.030
1.046
3.013
1.105
4.107
1.024
1.028
1.000
5.039
NAME XS-1-38-A1EXPNO 1PROCNO 1Date_ 20101006Time 11.02INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 8DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 80.6DW 60.800 usecDE 6.50 usecTE 297.9 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.00 usecPL1 -1.00 dBPL1W 13.56617069 WSFO1 400.1924713 MHzSI 32768SF 400.1900144 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-38-A1EXPNO 2PROCNO 1Date_ 20101006Time 11.09INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 500DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 228DW 20.800 usecDE 6.50 usecTE 298.4 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.90 usecPL1 -2.00 dBPL1W 55.33689499 WSFO1 100.6379183 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -1.00 dBPL12 15.16 dBPL13 18.62 dBPL2W 13.56617069 WPL12W 0.32844096 WPL13W 0.14806664 WSFO2 400.1916008 MHzSI 32768SF 100.6278430 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
12.182
21.198
27.050
33.085
33.885
36.092
38.053
47.557
51.384
64.166
64.386
71.041
71.406
76.843
77.160
77.478
111.367
127.745
127.861
128.495
135.193
138.669
140.624
167.277
Bruker Advance III 400
46
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
1.1064
1.2222
1.4945
1.5024
1.5074
1.5159
1.5281
1.5362
1.5413
1.5496
1.6065
1.6313
1.6556
1.6645
1.6878
1.6970
1.7049
1.7168
1.7248
1.7290
1.8771
1.8897
1.9103
1.9230
1.9434
1.9559
2.0486
2.0603
2.0777
2.0892
2.1004
2.1065
2.1129
2.1160
2.1222
2.1282
2.3298
2.3343
2.3481
2.3529
2.3600
2.3659
2.3716
2.3787
2.3836
2.3973
2.7368
2.7489
2.7521
2.7642
2.7805
2.7925
2.7958
2.8079
3.7449
3.7608
3.7666
3.7738
3.7825
3.7897
3.7955
3.8114
3.8808
3.8922
3.9011
3.9038
3.9061
3.9130
3.9171
3.9341
3.9460
3.9481
3.9535
3.9608
3.9673
4.0558
4.0982
4.1291
4.4149
4.4433
4.6605
4.6890
5.5210
5.5284
5.5317
5.5389
7.2604
7.2683
7.2790
7.2900
7.3001
7.3100
7.3164
7.3194
7.3247
7.3381
7.3491
3.004
3.067
1.105
1.121
2.010
1.028
2.053
1.004
1.001
1.029
4.067
2.058
1.001
1.004
1.000
5.075
NAME XS-1-35-A1EXPNO 3PROCNO 1Date_ 20101008Time 20.31INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zg30TD 65536SOLVENT CDCl3NS 11DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 203DW 60.800 usecDE 6.50 usecTE 294.5 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 7.10 usecPL1 -2.00 dBPL1W 13.17734718 WSFO1 400.1324710 MHzSI 32768SF 400.1300051 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-35-A1EXPNO 4PROCNO 1Date_ 20101008Time 20.44INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zgpg30TD 65536SOLVENT CDCl3NS 500DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 294.7 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 14.50 usecPL1 -4.00 dBPL1W 90.22689819 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -2.00 dBPL12 18.80 dBPL13 18.80 dBPL2W 13.17734718 WPL12W 0.10960442 WPL13W 0.10960442 WSFO2 400.1316005 MHzSI 32768SF 100.6127553 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
12.143
21.927
26.982
33.250
33.462
36.145
37.983
47.187
62.719
64.183
64.362
70.747
72.165
76.842
77.160
77.477
111.487
119.909
127.640
127.864
128.447
138.873
146.326
Bruker Advance III 400
47
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
0.9960
1.0147
1.1020
1.4986
1.5030
1.5325
1.5368
1.6158
1.6476
1.6561
1.6810
1.6863
1.7052
1.7134
1.8781
1.8912
1.9111
1.9243
1.9440
1.9569
2.0467
2.0582
2.0757
2.0870
2.1000
2.1219
2.3312
2.3453
2.3493
2.3628
2.3758
2.3799
2.3944
2.7365
2.7494
2.7633
2.7801
2.7931
2.8070
3.3634
3.7481
3.7644
3.7695
3.7769
3.7856
3.7930
3.7981
3.8143
3.8799
3.8913
3.9017
3.9127
3.9317
3.9454
3.9582
4.0131
4.0439
4.4098
4.4383
4.6119
4.6556
4.6841
5.5519
7.2605
7.2757
7.2866
7.2968
7.3353
7.3462
3.128
3.188
1.055
2.041
1.095
2.175
1.071
1.044
3.081
1.087
5.181
1.109
1.054
2.127
1.060
1.000
5.252
NAME XS-36-A1EXPNO 1PROCNO 1Date_ 20101004Time 17.20INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zg30TD 65536SOLVENT CDCl3NS 14DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 90.5DW 60.800 usecDE 6.50 usecTE 294.4 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 7.10 usecPL1 -2.00 dBPL1W 13.17734718 WSFO1 400.1324710 MHzSI 32768SF 400.1300051 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-36-A1EXPNO 2PROCNO 1Date_ 20101004Time 17.28INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zgpg30TD 65536SOLVENT CDCl3NS 500DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 294.9 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 14.50 usecPL1 -4.00 dBPL1W 90.22689819 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 80.00 usecPL2 -2.00 dBPL12 18.80 dBPL13 18.80 dBPL2W 13.17734718 WPL12W 0.10960442 WPL13W 0.10960442 WSFO2 400.1316005 MHzSI 32768SF 100.6127557 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
12.145
21.692
27.003
33.358
33.468
36.127
37.947
47.145
55.495
64.177
64.346
67.203
70.712
72.111
76.843
77.160
77.477
95.648
111.513
122.090
127.620
127.867
128.431
138.890
142.702
Bruker Advance III 400
48
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
0.6673
1.1074
1.1263
1.3382
1.3464
1.3566
1.3641
1.3721
1.3822
1.3902
1.4634
1.4716
1.4826
1.4947
1.5064
1.5144
1.5228
1.5512
1.5687
1.5800
1.6051
1.6151
1.6378
1.6483
1.8486
1.8576
1.8802
1.8905
1.9149
1.9264
2.0281
2.0401
2.0560
2.0680
2.6117
2.6259
2.6304
2.6382
2.6437
2.6493
2.6570
2.6614
2.7455
2.7570
2.7685
2.7749
2.7864
2.7979
3.0909
3.3398
3.3466
3.3611
3.3719
3.3887
3.3997
3.4186
3.4281
3.4343
3.4485
3.4524
3.4606
3.4646
3.4719
3.4739
3.4787
3.4870
3.4909
3.5024
3.5180
3.5302
3.5484
3.5550
3.5731
3.6806
3.6887
3.7054
3.7135
3.7997
3.8067
3.8118
3.8189
3.8277
3.8351
3.8451
3.8540
3.8608
3.8660
3.8728
4.1414
4.1702
4.2903
4.5118
4.5403
7.0633
7.0816
7.1000
7.1463
7.1601
7.1789
7.1831
7.3008
7.3191
3.083
3.149
1.208
4.381
1.167
1.091
1.154
1.089
3.118
1.036
7.267
1.018
1.114
1.137
2.000
1.289
1.122
1.131
1.067
2.150
NAME XS-1-37-A1EXPNO 3PROCNO 1Date_ 20101027Time 17.38INSTRUM spectPROBHD 5 mm PADUL 13CPULPROG zg30TD 65536SOLVENT C6D6NS 8DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 203DW 60.800 usecDE 6.50 usecTE 295.0 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.83 usecPL1 0.00 dBPL1W 8.31434441 WSFO1 400.1324710 MHzSI 32768SF 400.1300444 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-37-A1EXPNO 4PROCNO 1Date_ 20101027Time 18.08INSTRUM spectPROBHD 5 mm PADUL 13CPULPROG zgpg30TD 65536SOLVENT C6D6NS 500DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 295.5 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.68 usecPL1 -0.60 dBPL1W 41.24164963 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 0.00 dBPL12 15.66 dBPL13 15.92 dBPL2W 8.31434441 WPL12W 0.22585411 WPL13W 0.21272963 WSFO2 400.1316005 MHzSI 32768SF 100.6127436 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
12.551
16.649
27.140
36.218
36.392
36.723
41.597
50.770
55.183
55.999
64.075
64.247
67.784
69.796
70.525
73.084
96.648
111.393
127.590
127.819
127.996
128.059
128.300
128.540
139.625
Bruker Advance III 400
49
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
0.4773
0.9017
1.0951
1.1140
1.3790
1.4071
1.4350
1.4632
1.4680
1.4767
1.4882
1.4970
1.5050
1.5181
1.5304
1.5385
1.5435
1.5517
1.6612
1.6699
1.6790
1.6926
1.7010
1.7952
1.9092
1.9240
1.9422
1.9568
1.9736
1.9881
2.0103
2.0223
2.0384
2.0504
2.5772
2.5913
2.5961
2.6037
2.6093
2.6149
2.6224
2.6273
2.6413
2.8062
2.8181
2.8302
2.8341
2.8463
2.8582
3.1655
3.3919
3.4029
3.4187
3.4315
3.4471
3.4511
3.4594
3.4611
3.4709
3.4755
3.4854
3.4906
3.4947
3.5006
3.5042
3.5156
3.5729
3.5817
4.0380
4.0667
4.3890
4.4055
4.4162
4.4333
4.4493
5.2349
5.2474
5.2636
5.2761
5.2924
5.3049
7.0581
7.0764
7.0947
7.1404
7.1631
7.1772
7.2793
7.2975
1.359
2.977
2.990
3.171
1.990
2.976
1.069
1.070
1.055
1.000
2.883
5.211
1.935
1.030
3.062
1.000
1.038
1.001
1.283
2.019
NAME XS-1-39-A1EXPNO 7PROCNO 1Date_ 20101025Time 21.19INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT C6D6NS 16DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 101DW 60.800 usecDE 6.50 usecTE 297.9 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.00 usecPL1 -1.00 dBPL1W 13.56617069 WSFO1 400.1924713 MHzSI 32768SF 400.1900000 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-39-A1EXPNO 8PROCNO 1Date_ 20101025Time 21.32INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT C6D6NS 615DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 298.4 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.90 usecPL1 -2.00 dBPL1W 55.33689499 WSFO1 100.6379183 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -1.00 dBPL12 15.16 dBPL13 18.62 dBPL2W 13.56617069 WPL12W 0.32844096 WPL13W 0.14806664 WSFO2 400.1916008 MHzSI 32768SF 100.6278192 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
12.363
16.831
20.937
27.098
36.518
36.616
36.778
38.198
50.739
54.431
55.034
64.082
64.236
64.488
69.605
70.801
73.065
96.806
111.406
127.590
127.820
127.939
128.062
128.178
128.303
128.547
139.527
169.942
Bruker Advance III 400
50
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
0.6471
1.1869
1.2058
1.9874
1.2874
1.3062
1.3264
1.3350
1.3431
1.3549
1.3635
1.3718
1.3936
1.3979
1.4280
1.4318
1.5342
1.5501
1.5647
1.5721
1.5997
1.6268
1.6594
1.7448
1.7668
1.7825
1.8003
1.8156
1.8311
1.8462
1.9988
2.0165
2.0280
2.2712
2.2966
2.3018
2.3155
2.3193
2.9363
2.9489
2.9627
2.9774
2.9900
3.1203
3.4405
3.4486
3.4753
3.4810
3.4948
3.4968
3.5032
4.3213
4.3375
4.3626
4.3787
4.9165
4.9293
4.9447
4.9576
4.9731
4.9858
5.1197
5.1325
5.1484
5.1610
5.1770
5.1896
7.1601
3.029
2.988
2.292
3.353
2.813
1.173
1.125
3.037
1.201
1.031
2.833
6.288
0.942
1.027
1.000
1.020
NAME XS-1-43-A1EXPNO 2PROCNO 1Date_ 20111129Time 20.15INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zg30TD 65536SOLVENT C6D6NS 4DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 25.4DW 60.800 usecDE 6.50 usecTE 294.7 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 7.10 usecPL1 -2.00 dBPL1W 13.17734718 WSFO1 400.1324710 MHzSI 32768SF 400.1300438 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-43-A1EXPNO 3PROCNO 1Date_ 20111129Time 20.22INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zgpg30TD 65536SOLVENT C6D6NS 202DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 294.9 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 14.50 usecPL1 -4.00 dBPL1W 90.22689819 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -2.00 dBPL12 20.06 dBPL13 22.00 dBPL2W 13.17734718 WPL12W 0.08200268 WPL13W 0.05245997 WSFO2 400.1316005 MHzSI 32768SF 100.6127444 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
12.062
16.096
20.761
26.593
36.382
36.706
36.866
38.866
39.495
49.581
53.989
55.025
64.166
64.292
68.598
76.876
96.677
110.931
127.819
128.059
128.300
169.694
Bruker Advance III 400
51
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
0.5011
0.5254
0.9463
0.9582
0.9805
0.9925
1.0181
1.0275
1.0526
1.0720
1.3151
1.3294
1.3435
1.3580
1.5264
1.5546
1.5670
1.5861
1.5930
1.6008
1.7157
1.9896
2.0236
2.0279
2.1077
2.1259
2.1476
2.1762
2.1990
2.6866
2.7030
2.7216
2.7400
2.7558
2.9911
3.0037
3.0193
3.0326
3.0464
3.1138
3.3095
3.3174
3.3363
3.3458
3.3572
3.3734
3.3839
4.2929
4.3091
4.3343
4.3504
4.7653
4.7781
4.7933
4.8061
4.8214
4.8341
5.0340
5.0464
5.0627
5.0751
5.0914
5.1039
7.1600
3.040
2.097
3.208
1.086
2.139
3.169
1.142
3.141
1.049
1.007
1.155
3.017
2.029
0.993
0.953
1.020
1.000
NAME XS-1-44-A1EXPNO 11PROCNO 1Date_ 20120303Time 10.24INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT C6D6NS 16DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 114DW 60.800 usecDE 6.50 usecTE 298.9 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.00 usecPL1 -1.00 dBPL1W 13.56617069 WSFO1 400.1924713 MHzSI 32768SF 400.1900013 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-44-A1EXPNO 12PROCNO 1Date_ 20120303Time 10.40INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT C6D6NS 871DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 228DW 20.800 usecDE 6.50 usecTE 299.1 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.90 usecPL1 -2.00 dBPL1W 55.33689499 WSFO1 100.6379183 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -1.00 dBPL12 15.16 dBPL13 18.62 dBPL2W 13.56617069 WPL12W 0.32844096 WPL13W 0.14806664 WSFO2 400.1916008 MHzSI 32768SF 100.6278192 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
13.442
15.501
20.660
33.795
36.538
37.964
38.616
39.319
43.700
50.754
53.313
55.110
64.096
68.065
74.966
96.720
127.818
128.060
128.301
169.471
210.868
Bruker Advance III 400
52
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
0.5044
0.5686
1.2020
1.2216
1.3529
1.3629
1.3734
1.3807
1.3912
1.4012
1.4630
1.4803
1.5159
1.5439
1.6920
1.7161
1.7300
1.7452
1.7591
2.2022
2.7436
2.7628
2.7772
2.7820
2.7964
2.8157
2.9716
2.9844
2.9980
2.9999
3.0137
3.0264
3.0943
3.4013
3.4117
4.2774
4.2937
4.3189
4.3351
4.8051
4.8176
4.8330
4.8458
4.8611
4.8738
4.9374
4.9505
4.9658
4.9788
4.9942
5.0072
5.8503
5.8762
6.7548
6.7807
7.1600
2.849
2.911
1.130
1.294
2.946
1.120
3.208
0.953
1.052
3.153
2.019
1.079
1.039
0.986
1.074
1.014
1.000
NAME XS-1-46-A1EXPNO 5PROCNO 1Date_ 20111205Time 15.39INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zg30TD 65536SOLVENT C6D6NS 4DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 71.8DW 60.800 usecDE 6.50 usecTE 295.1 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 7.10 usecPL1 -2.00 dBPL1W 13.17734718 WSFO1 400.1324710 MHzSI 32768SF 400.1300440 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-46-A1EXPNO 6PROCNO 1Date_ 20111205Time 15.48INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zgpg30TD 65536SOLVENT C6D6NS 312DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 295.3 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 14.50 usecPL1 -4.00 dBPL1W 90.22689819 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -2.00 dBPL12 20.06 dBPL13 22.00 dBPL2W 13.17734718 WPL12W 0.08200268 WPL13W 0.05245997 WSFO2 400.1316005 MHzSI 32768SF 100.6127444 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
13.834
17.638
20.586
38.470
39.115
39.193
39.755
48.920
49.752
55.198
63.934
67.794
74.148
96.598
126.645
127.819
128.059
128.300
154.484
169.489
199.814
Bruker Advance III 400
53
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm0.8796
1.3803
2.0446
2.0570
2.0674
2.0798
2.3630
2.3869
3.1601
3.4449
3.4580
3.4705
3.4831
3.5561
3.5697
3.5811
3.5947
4.0640
4.4275
4.9233
4.9272
4.9535
4.9589
4.9693
4.9794
5.5312
5.5561
5.5732
5.5813
5.5978
5.6232
6.0283
6.0522
6.3120
6.3166
6.3360
6.3406
7.1600
3.129
3.099
1.019
1.000
3.034
1.949
0.970
1.001
2.011
2.023
0.992
0.978
1.000
NAME XS-1-91-A1EXPNO 1PROCNO 1Date_ 20110409Time 10.48INSTRUM spectPROBHD 5 mm PADUL 13CPULPROG zg30TD 65536SOLVENT C6D6NS 8DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 80.6DW 60.800 usecDE 6.50 usecTE 294.1 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.83 usecPL1 0.00 dBPL1W 8.31434441 WSFO1 400.1324710 MHzSI 32768SF 400.1300438 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-91-A1EXPNO 2PROCNO 1Date_ 20110409Time 10.56INSTRUM spectPROBHD 5 mm PADUL 13CPULPROG zgpg30TD 65536SOLVENT C6D6NS 202DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 294.6 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.68 usecPL1 -0.60 dBPL1W 41.24164963 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 0.00 dBPL12 15.66 dBPL13 15.92 dBPL2W 8.31434441 WPL12W 0.22585411 WPL13W 0.21272963 WSFO2 400.1316005 MHzSI 32768SF 100.6127444 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
128.343
18.448
18.667
46.092
54.856
55.358
60.891
64.256
67.799
81.943
96.933
120.163
127.817
128.058
128.299
134.074
158.441
200.783
Bruker Advance III 400
54
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm0.5856
0.9387
1.4484
1.9159
1.9219
1.9260
1.9320
3.0430
3.0923
3.0973
3.1158
3.1208
3.2981
3.3040
3.3234
3.3293
3.7788
3.7891
3.8041
3.8144
4.2062
4.9910
4.9957
5.0062
5.0097
5.0165
5.0213
5.0484
5.0521
5.6247
5.6496
5.6670
5.6745
5.6917
5.6988
5.7161
6.0051
6.0105
6.0292
6.0346
7.1598
3.156
3.148
1.011
3.060
1.040
1.061
1.053
1.921
2.123
2.004
1.000
NAME XS-1-51-A1EXPNO 1PROCNO 1Date_ 20101203Time 18.57INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT C6D6NS 8DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 71.8DW 60.800 usecDE 6.50 usecTE 297.5 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.00 usecPL1 -1.00 dBPL1W 13.56617069 WSFO1 400.1924713 MHzSI 32768SF 400.1900014 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
PC 1.40GB 0LB 1.00 HzSSB 0WDW EMSF 100.6278192 MHzSI 32768SFO2 400.1916008 MHzPL13W 0.14806664 WPL12W 0.32844096 WPL2W 13.56617069 WPL13 18.62 dBPL12 15.16 dBPL2 −1.00 dBPCPD2 90.00 usecNUC2 1HCPDPRG2 waltz16======== CHANNEL f2 ========
SFO1 100.6379183 MHzPL1W 55.33689499 WPL1 −2.00 dBP1 9.90 usecNUC1 13C======== CHANNEL f1 ========
TD0 1D11 0.03000000 secD1 2.00000000 secTE 298.0 KDE 6.50 usecDW 20.800 usecRG 203AQ 1.3631988 secFIDRES 0.366798 HzSWH 24038.461 HzDS 4NS 203SOLVENT C6D6TD 65536PULPROG zgpg30PROBHD 5 mm PABBO BB−INSTRUM spectTime 19.02Date_ 20101203PROCNO 1EXPNO 2NAME XS−1−51−A1
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
13.792
17.854
44.008
54.970
55.283
64.516
65.247
69.469
96.508
121.427
127.063
127.821
128.062
128.303
132.704
157.850
192.449
210.667
Bruker Advance III 400
55
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm1.0377
1.2866
1.4007
1.4187
1.9992
2.0053
2.0106
2.0168
2.8056
2.8298
3.0782
3.3214
3.3276
3.3465
3.3527
3.6378
3.6469
3.6529
3.6620
3.7255
3.7371
3.7506
3.7622
4.2461
5.0405
5.0463
5.0659
5.0718
5.1013
5.1068
5.1440
5.1495
5.4489
5.4727
5.5623
5.5715
5.5862
5.5954
6.1258
6.1507
6.1685
6.1754
6.1934
6.2182
7.1600
3.141
3.164
1.001
1.015
1.020
3.047
1.052
1.019
1.041
2.058
1.022
1.053
1.020
1.014
1.000
NAME XS-1-105-A1EXPNO 1PROCNO 1Date_ 20110426Time 19.34INSTRUM spectPROBHD 5 mm PADUL 13CPULPROG zg30TD 65536SOLVENT C6D6NS 8DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 161DW 60.800 usecDE 6.50 usecTE 294.5 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.83 usecPL1 0.00 dBPL1W 8.31434441 WSFO1 400.1324710 MHzSI 32768SF 400.1300441 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-105-A1EXPNO 3PROCNO 1Date_ 20110426Time 20.29INSTRUM spectPROBHD 5 mm PADUL 13CPULPROG zgpg30TD 65536SOLVENT C6D6NS 178DS 4SWH 26041.666 HzFIDRES 0.397364 HzAQ 1.2583412 secRG 203DW 19.200 usecDE 6.50 usecTE 295.0 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.68 usecPL1 -0.60 dBPL1W 41.24164963 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 0.00 dBPL12 15.66 dBPL13 15.92 dBPL2W 8.31434441 WPL12W 0.22585411 WPL13W 0.21272963 WSFO2 400.1316005 MHzSI 32768SF 100.6127439 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
16.458
18.374
42.721
55.184
56.243
57.096
58.935
65.680
70.627
96.493
118.551
127.816
128.057
128.298
135.898
140.824
219.712
Bruker Advance III 400
56
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
-0.0392
-0.0114
0.2949
0.4398
0.9439
1.1154
1.3393
2.0870
2.0931
2.0987
2.1048
2.8356
2.8605
3.1067
3.4016
3.4076
3.4267
3.4327
3.7657
3.7778
3.7908
3.8029
3.8311
4.2803
5.1180
5.1383
5.1442
5.1597
5.1654
5.5121
6.3500
6.3754
6.3916
6.4013
6.4170
6.4427
7.1601
2.898
2.819
9.184
3.153
3.106
1.005
1.063
2.983
1.043
1.025
0.904
2.077
0.940
1.020
2.017
1.000
NAME XS-1-54-A1EXPNO 1PROCNO 1Date_ 20101218Time 16.38INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT C6D6NS 16DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 101DW 60.800 usecDE 6.50 usecTE 297.2 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.00 usecPL1 -1.00 dBPL1W 13.56617069 WSFO1 400.1924713 MHzSI 32768SF 400.1900014 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-54-A1EXPNO 3PROCNO 1Date_ 20101218Time 17.26INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT C6D6NS 841DS 4SWH 28409.092 HzFIDRES 0.433488 HzAQ 1.1534836 secRG 181DW 17.600 usecDE 6.50 usecTE 297.5 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.90 usecPL1 -2.00 dBPL1W 55.33689499 WSFO1 100.6379183 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -1.00 dBPL12 15.16 dBPL13 18.62 dBPL2W 13.56617069 WPL12W 0.32844096 WPL13W 0.14806664 WSFO2 400.1916008 MHzSI 32768SF 100.6278197 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
220 200 180 160 140 120 100 80 60 40 20 0 ppm
-5.004
-4.353
1.414
17.343
18.227
18.480
25.921
42.872
55.199
57.178
59.290
65.748
70.801
96.559
117.057
127.818
128.059
128.300
136.891
140.493
219.833
Bruker Advance III 400
57
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
0.0295
0.0615
0.2956
0.4385
0.9934
1.1373
1.2929
2.2807
2.3057
2.5859
2.5980
2.6024
2.6145
3.1764
3.4082
3.4200
3.4332
3.4450
3.5543
3.5713
3.5793
3.5963
3.7038
4.4471
5.0627
5.0691
5.1081
5.1124
5.1164
5.1235
5.1424
5.1492
5.1540
5.1576
5.5827
6.3185
6.3438
6.3610
6.3690
6.3863
6.4116
7.1601
3.078
3.037
9.262
3.113
3.034
0.955
0.908
2.984
0.943
1.006
0.969
1.978
4.079
2.039
1.000
NAME XS-1-124-A1EXPNO 1PROCNO 1Date_ 20110617Time 11.04INSTRUM spectPROBHD 5 mm PADUL 13CPULPROG zg30TD 65536SOLVENT C6D6NS 7DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 161DW 60.800 usecDE 6.50 usecTE 294.6 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.83 usecPL1 0.00 dBPL1W 8.31434441 WSFO1 400.1324710 MHzSI 32768SF 400.1300441 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-124-A1EXPNO 3PROCNO 1Date_ 20110617Time 11.25INSTRUM spectPROBHD 5 mm PADUL 13CPULPROG zgpg30TD 65536SOLVENT C6D6NS 713DS 4SWH 26041.666 HzFIDRES 0.397364 HzAQ 1.2583412 secRG 203DW 19.200 usecDE 6.50 usecTE 294.6 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.68 usecPL1 -0.60 dBPL1W 41.24164963 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 0.00 dBPL12 15.66 dBPL13 15.92 dBPL2W 8.31434441 WPL12W 0.22585411 WPL13W 0.21272963 WSFO2 400.1316005 MHzSI 32768SF 100.6127432 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
-4.875
-4.074
18.294
19.483
21.404
26.025
44.544
51.111
54.756
55.152
58.281
70.097
75.729
96.811
110.004
116.190
127.820
128.060
128.302
138.195
139.466
159.576
Bruker Advance III 400
58
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
0.0198
0.0531
0.2984
0.4155
0.9857
1.0324
1.2313
2.2008
2.2258
2.3220
2.3370
2.3516
3.2793
3.2914
3.3056
3.3193
3.3320
3.4521
3.4666
3.4805
3.4944
3.5104
3.6607
3.6684
5.0090
5.0122
5.0306
5.0344
5.0744
5.0801
5.0945
5.1010
5.1199
5.1263
5.5026
5.5054
5.5266
5.5294
5.5349
5.5429
5.5588
5.5667
6.2844
6.3096
6.3270
6.3348
6.3521
6.3774
7.1600
3.197
3.020
9.177
3.069
3.081
1.057
0.973
1.056
1.044
0.950
4.199
2.111
1.000
NAME XS-1-127-A1(H1)EXPNO 1PROCNO 1Date_ 20120110Time 19.44INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zg30TD 65536SOLVENT C6D6NS 6DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 203DW 60.800 usecDE 6.50 usecTE 295.4 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 7.10 usecPL1 -2.00 dBPL1W 13.17734718 WSFO1 400.1324710 MHzSI 32768SF 400.1300442 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-127-A1EXPNO 2PROCNO 1Date_ 20110908Time 19.56INSTRUM spectPROBHD 5 mm PADUL 13CPULPROG zgpg30TD 65536SOLVENT C6D6NS 349DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 295.0 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.68 usecPL1 -0.60 dBPL1W 41.24164963 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 0.00 dBPL12 15.66 dBPL13 15.92 dBPL2W 8.31434441 WPL12W 0.22585411 WPL13W 0.21272963 WSFO2 400.1316005 MHzSI 32768SF 100.6127436 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
-4.895
-4.080
18.282
19.135
21.257
26.007
44.453
51.209
56.862
58.255
63.915
75.778
109.833
116.228
127.626
127.819
128.060
128.301
138.040
139.452
159.478
Bruker Advance III 400
59
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
-0.0248
0.0146
0.4977
0.9279
0.9447
0.9535
1.8100
1.8198
1.8287
1.8385
2.2690
2.2802
2.3213
2.3325
2.4013
2.4264
2.4460
2.4601
2.4669
2.4809
3.4381
3.4480
3.4591
3.4678
3.4770
3.4881
3.4980
3.5225
3.5309
3.6507
3.6649
3.6695
3.6830
3.6941
3.6984
3.7126
5.0027
5.0087
5.0507
5.0562
5.0759
5.0820
5.4272
5.4514
5.4698
5.4784
5.4934
5.5021
6.1559
6.1811
6.1984
6.2063
6.2236
6.2488
7.1600
2.970
2.917
3.135
3.011
9.167
1.000
1.036
0.998
1.038
0.978
1.084
0.995
1.168
2.211
2.107
1.018
NAME XS-1-130-A1EXPNO 1PROCNO 1Date_ 20110629Time 22.41INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT C6D6NS 16DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 90.5DW 60.800 usecDE 6.50 usecTE 297.7 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.00 usecPL1 -1.00 dBPL1W 13.56617069 WSFO1 400.1924713 MHzSI 32768SF 400.1900016 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-130-A1EXPNO 2PROCNO 1Date_ 20110630Time 3.27INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT C6D6NS 5000DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 161DW 20.800 usecDE 6.50 usecTE 299.0 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.90 usecPL1 -2.00 dBPL1W 55.33689499 WSFO1 100.6379183 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -1.00 dBPL12 15.16 dBPL13 18.62 dBPL2W 13.56617069 WPL12W 0.32844096 WPL13W 0.14806664 WSFO2 400.1916008 MHzSI 32768SF 100.6278192 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
-4.972
-4.029
16.085
18.237
19.093
25.948
44.151
48.518
48.674
53.258
58.101
61.455
69.170
72.844
116.765
126.692
127.819
128.060
128.301
137.318
139.594
Bruker Advance III 400
60
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
0.0597
0.0655
0.4547
0.8859
0.9950
1.0680
1.1415
1.6028
1.6135
1.6254
1.6361
1.8717
1.8849
1.8981
2.1228
2.4692
2.4944
3.4975
3.5091
3.5236
3.5363
3.5481
3.5812
3.5944
3.6039
3.6074
3.6171
3.6304
3.6436
3.7888
3.7976
5.0376
5.0439
5.0704
5.0774
5.0859
5.0962
5.1028
5.4373
5.4402
5.4612
5.4641
5.4804
5.4893
5.5040
5.5129
6.2233
6.2488
6.2654
6.2743
6.2910
6.3166
7.1602
2.954
2.947
3.135
9.339
3.065
3.154
1.036
0.971
1.000
1.009
1.045
1.045
1.019
2.071
2.044
1.000
NAME XS-1-128-A1EXPNO 12PROCNO 1Date_ 20110701Time 11.36INSTRUM spectPROBHD 5 mm PADUL 13CPULPROG zg30TD 65536SOLVENT C6D6NS 8DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 203DW 60.800 usecDE 6.50 usecTE 296.2 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.83 usecPL1 0.00 dBPL1W 8.31434441 WSFO1 400.1324710 MHzSI 32768SF 400.1300447 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-128-A1EXPNO 13PROCNO 1Date_ 20110701Time 11.41INSTRUM spectPROBHD 5 mm PADUL 13CPULPROG zgpg30TD 65536SOLVENT C6D6NS 2525DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 296.3 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.68 usecPL1 -0.60 dBPL1W 41.24164963 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 0.00 dBPL12 15.66 dBPL13 15.92 dBPL2W 8.31434441 WPL12W 0.22585411 WPL13W 0.21272963 WSFO2 400.1316005 MHzSI 32768SF 100.6127429 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
-4.877
-3.965
16.139
18.310
19.267
26.052
27.476
43.760
53.586
57.590
59.309
61.835
70.467
81.759
115.913
126.062
127.822
128.063
128.304
138.501
140.630
Bruker Advance III 400
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Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
0.0655
0.4661
0.9998
1.0655
1.1347
1.2300
1.5521
1.6173
1.6256
2.2232
2.7384
2.7636
2.9520
2.9725
3.7941
3.7985
4.2286
4.2328
4.2373
4.2427
4.2508
4.2621
4.2670
4.9835
4.9874
4.9912
5.0096
5.0134
5.0172
5.1088
5.1154
5.1294
5.1345
5.1407
5.1513
5.1552
5.1591
5.1717
5.1782
5.1943
5.1983
5.2021
5.4959
6.0517
6.0658
6.0777
6.0923
6.1090
6.1208
6.1350
6.2663
6.2916
6.3089
6.3169
6.3342
6.3595
7.1599
6.156
9.192
3.052
3.031
3.212
1.050
0.907
1.016
0.968
1.027
1.095
1.165
3.091
2.093
1.000
1.068
NAME XS-1-133-A1EXPNO 3PROCNO 1Date_ 20110729Time 20.34INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT C6D6NS 16DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 101DW 60.800 usecDE 6.50 usecTE 298.5 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.00 usecPL1 -1.00 dBPL1W 13.56617069 WSFO1 400.1924713 MHzSI 32768SF 400.1900019 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-131-A1EXPNO 2PROCNO 1Date_ 20110706Time 17.46INSTRUM spectPROBHD 5 mm PADUL 13CPULPROG zgpg30TD 65536SOLVENT C6D6NS 1828DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 295.2 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.68 usecPL1 -0.60 dBPL1W 41.24164963 WSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 0.00 dBPL12 15.66 dBPL13 15.92 dBPL2W 8.31434441 WPL12W 0.22585411 WPL13W 0.21272963 WSFO2 400.1316005 MHzSI 32768SF 100.6127436 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
-4.991
-4.061
15.905
18.240
18.961
25.969
26.380
44.497
53.798
58.398
69.836
70.051
82.759
116.589
126.873
127.818
128.058
128.299
137.195
138.662
201.083
Bruker Advance III 400
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Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
9 8 7 6 5 4 3 2 1 0 ppm
0.0532
0.0655
0.4661
0.9124
0.9629
0.9786
0.9998
1.0098
1.0307
1.0655
1.1347
1.2300
1.5521
1.6173
1.6256
2.1146
2.2232
2.7384
2.7636
2.9520
2.9725
3.7941
3.7985
4.2373
4.2427
4.2508
4.2621
4.9835
4.9874
4.9912
5.0096
5.0134
5.0172
5.1088
5.1154
5.1294
5.1345
5.1407
5.1513
5.1552
5.1591
5.1717
5.1782
5.1943
5.1983
5.2021
5.4959
6.0517
6.0658
6.0777
6.0923
6.1090
6.1208
6.1350
6.2663
6.2916
6.3089
6.3169
6.3342
6.3595
7.1599
6.156
9.192
3.052
3.031
3.212
1.050
1.015
1.016
0.968
1.027
1.095
1.165
3.091
2.093
1.000
1.068
NAME XS-1-133-A1EXPNO 3PROCNO 1Date_ 20110729Time 20.34INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT C6D6NS 16DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 101DW 60.800 usecDE 6.50 usecTE 298.5 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.00 usecPL1 -1.00 dBPL1W 13.56617069 WSFO1 400.1924713 MHzSI 32768SF 400.1900019 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-133-A1EXPNO 4PROCNO 1Date_ 20110729Time 20.42INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT C6D6NS 8000DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 161DW 20.800 usecDE 6.50 usecTE 298.8 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.90 usecPL1 -2.00 dBPL1W 55.33689499 WSFO1 100.6379183 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -1.00 dBPL12 15.16 dBPL13 18.62 dBPL2W 13.56617069 WPL12W 0.32844096 WPL13W 0.14806664 WSFO2 400.1916008 MHzSI 32768SF 100.6278192 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
-4.862
-3.958
16.280
18.314
20.245
25.976
26.048
27.195
30.086
44.908
53.898
58.110
62.273
70.438
74.185
84.348
113.931
116.097
125.947
127.819
128.060
128.301
138.741
141.497
143.196
Bruker Advance III 400
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Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm3.6506
0.0447
0.0533
0.4306
0.8724
0.9704
1.2634
1.3026
1.5858
1.6023
1.7147
1.7261
1.7589
1.7702
2.2609
2.3050
2.6060
2.6312
3.6397
3.6476
3.6585
3.7739
3.7836
3.8864
3.8939
3.9028
3.9103
5.0601
5.0660
5.0852
5.0911
5.2017
5.2071
5.2442
5.2498
5.3846
5.4084
5.5092
5.5191
5.5329
5.5429
6.1790
6.2041
6.2217
6.2294
6.2468
6.2719
7.1600
2.913
2.944
3.059
9.024
3.060
3.031
1.053
1.047
1.026
1.024
1.087
1.030
1.000
1.132
1.079
1.033
1.076
1.089
NAME XS-1-134-A1EXPNO 11PROCNO 1Date_ 20110928Time 14.36INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT C6D6NS 16DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 128DW 60.800 usecDE 6.50 usecTE 298.8 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.00 usecPL1 -1.00 dBPL1W 13.56617069 WSFO1 400.1924713 MHzSI 32768SF 400.1900012 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-134-A1EXPNO 14PROCNO 1Date_ 20111001Time 2.58INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT C6D6NS 5000DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 71.8DW 20.800 usecDE 6.50 usecTE 300.1 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.90 usecPL1 -2.00 dBPL1W 55.33689499 WSFO1 100.6379183 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -1.00 dBPL12 15.16 dBPL13 18.62 dBPL2W 13.56617069 WPL12W 0.32844096 WPL13W 0.14806664 WSFO2 400.1916008 MHzSI 32768SF 100.6278189 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
-4.932
-3.977
16.159
18.287
19.894
20.644
25.976
34.514
44.980
51.874
57.781
62.778
70.094
78.096
85.285
94.711
116.858
126.859
127.819
128.060
128.301
137.140
139.659
173.868
Bruker Advance III 400
64
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
0.0246
0.0512
0.4346
0.9536
0.9740
1.3045
1.3596
1.7018
1.7189
1.9606
1.9788
2.6976
2.7229
3.7984
3.8080
4.0492
4.0577
4.0664
4.0748
4.1361
4.1442
5.0435
5.0494
5.0687
5.0745
5.1622
5.1675
5.2049
5.2101
5.4086
5.4324
5.5244
5.5342
5.5481
5.5579
5.9308
5.9487
5.9669
5.9850
6.1826
6.2078
6.2253
6.2330
6.2505
6.2757
7.1600
3.013
3.035
9.006
3.077
3.062
3.036
1.062
3.029
1.049
1.104
1.071
1.049
1.086
1.055
1.078
1.086
1.000
1.043
NAME XS-1-142-A1EXPNO 1PROCNO 1Date_ 20120403Time 11.02INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT C6D6NS 16DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 114DW 60.800 usecDE 6.50 usecTE 298.9 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.00 usecPL1 -1.00 dBPL1W 13.56617069 WSFO1 400.1924713 MHzSI 32768SF 400.1900013 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-142-A1EXPNO 2PROCNO 1Date_ 20120403Time 21.16INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT C6D6NS 12488DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 299.3 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.90 usecPL1 -2.00 dBPL1W 55.33689499 WSFO1 100.6379183 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -1.00 dBPL12 15.16 dBPL13 18.62 dBPL2W 13.56617069 WPL12W 0.32844096 WPL13W 0.14806664 WSFO2 400.1916008 MHzSI 32768SF 100.6278192 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
-4.927
-3.985
14.138
16.246
18.277
20.085
21.094
25.976
45.163
52.007
57.837
62.912
70.136
81.257
83.552
95.333
116.798
126.777
127.164
127.818
128.059
128.300
137.166
139.783
142.688
167.844
Bruker Advance III 400
65
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
0.0167
0.0450
0.4222
0.9495
0.9632
1.2635
1.3841
1.3999
1.4178
1.7400
1.7577
2.6292
2.6546
6.6946
6.6969
6.7483
6.7506
3.7837
3.7934
4.0708
4.0800
4.0886
4.0978
4.3867
4.3942
5.0347
5.0407
5.0598
5.0658
5.1332
5.1388
5.1759
5.1814
5.4143
5.4379
5.5225
5.5324
5.5462
5.5561
6.1737
6.1989
6.2164
6.2241
6.2416
6.2668
6.7127
6.7149
6.7305
6.7327
7.1607
3.053
2.977
9.262
3.135
3.208
3.089
3.207
1.105
1.090
1.075
1.156
1.084
1.104
1.131
1.107
1.107
1.148
1.000
NAME XS-1-135-A1EXPNO 10PROCNO 1Date_ 20111208Time 21.25INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT C6D6NS 16DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 144DW 60.800 usecDE 6.50 usecTE 298.9 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.00 usecPL1 -1.00 dBPL1W 13.56617069 WSFO1 400.1924713 MHzSI 32768SF 400.1900009 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-135-A1EXPNO 11PROCNO 1Date_ 20111208Time 21.31INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT C6D6NS 12045DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 299.6 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.90 usecPL1 -2.00 dBPL1W 55.33689499 WSFO1 100.6379183 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -1.00 dBPL12 15.16 dBPL13 18.62 dBPL2W 13.56617069 WPL12W 0.32844096 WPL13W 0.14806664 WSFO2 400.1916008 MHzSI 32768SF 100.6278189 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
-4.947
-4.008
15.388
16.288
18.270
20.180
21.228
25.971
45.183
51.990
57.901
62.749
70.084
76.687
84.016
95.794
116.828
126.765
127.819
128.060
128.302
128.713
137.085
139.738
139.779
168.663
Bruker Advance III 400
66
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
3.5473
3.5754
0.4242
0.8396
1.1428
1.1635
1.2561
1.2827
1.6350
1.6517
1.9706
1.9888
2.6526
2.6763
3.5574
3.5663
3.9881
3.9965
4.0051
4.0135
4.0686
4.0768
4.9409
4.9461
4.9667
4.9718
5.0932
5.0969
5.1361
5.1397
5.3356
5.3592
5.5717
5.5817
5.5954
5.6055
5.8216
5.8467
5.8647
5.8709
5.8891
5.9145
5.9338
5.9518
5.9697
7.1600
3.032
1.003
3.083
3.145
1.082
3.054
0.986
1.157
1.027
0.982
1.049
1.073
1.048
1.000
2.156
NAME XS-1-143-A1EXPNO 1PROCNO 1Date_ 20120416Time 21.24INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT C6D6NS 16DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 128DW 60.800 usecDE 6.50 usecTE 299.6 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.00 usecPL1 -1.00 dBPL1W 13.56617069 WSFO1 400.1924713 MHzSI 32768SF 400.1900016 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-143-A1EXPNO 2PROCNO 1Date_ 20120416Time 22.36INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT C6D6NS 11006DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 181DW 20.800 usecDE 6.50 usecTE 299.9 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.90 usecPL1 -2.00 dBPL1W 55.33689499 WSFO1 100.6379183 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -1.00 dBPL12 15.16 dBPL13 18.62 dBPL2W 13.56617069 WPL12W 0.32844096 WPL13W 0.14806664 WSFO2 400.1916008 MHzSI 32768SF 100.6278188 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
14.128
15.431
19.977
20.847
45.005
51.958
56.301
62.744
69.900
81.145
83.529
95.298
119.127
127.143
127.374
127.819
128.060
128.301
135.619
139.737
142.675
167.824
Bruker Advance III 400
67
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm1.0358
1.1394
1.4163
1.5709
2.2458
2.2640
2.5232
2.5399
2.8141
2.8181
2.8378
2.8418
4.8388
4.8466
4.8646
4.8728
4.8813
4.8894
5.1532
5.1577
5.1783
5.1827
5.2200
5.4900
5.5145
5.5324
5.5391
5.5568
5.5815
5.8781
5.9021
6.6583
6.6697
6.6753
6.6940
6.7127
7.2599
3.005
3.106
3.143
3.015
0.991
0.973
0.973
1.026
2.101
1.033
1.000
2.084
NAME XS-1-144-A1EXPNO 11PROCNO 1Date_ 20120504Time 19.26INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zg30TD 65536SOLVENT CDCl3NS 32DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 203DW 60.800 usecDE 6.50 usecTE 294.2 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 7.10 usecPL1 -2.00 dBPL1W 13.17734718 WSFO1 400.1324710 MHzSI 32768SF 400.1300099 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-144-A1EXPNO 3PROCNO 1Date_ 20120417Time 22.06INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 11820DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 228DW 20.800 usecDE 6.50 usecTE 300.1 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.90 usecPL1 -2.00 dBPL1W 55.33689499 WSFO1 100.6379183 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -1.00 dBPL12 15.16 dBPL13 18.62 dBPL2W 13.56617069 WPL12W 0.32844096 WPL13W 0.14806664 WSFO2 400.1916008 MHzSI 32768SF 100.6278416 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
12.880
14.601
19.682
22.434
47.019
60.825
62.790
63.979
76.843
77.160
77.478
82.337
83.134
94.169
121.775
126.097
127.014
132.387
144.823
157.112
168.380
201.556
Bruker Advance III 400
68
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm
0.4318
0.8321
1.1351
1.1559
1.2314
1.3111
1.3799
1.3978
1.6653
1.6829
2.5945
2.6179
3.5241
3.5335
3.5430
3.5520
4.0022
4.0113
4.0198
4.0289
4.3123
4.3201
4.9357
4.9406
4.9614
4.9662
5.0695
5.0732
5.1126
5.1161
5.3382
5.3618
5.5684
5.5785
5.5921
5.6021
5.8154
5.8401
5.8585
5.8647
5.8830
5.9078
6.6974
6.7152
6.7333
6.7495
7.1600
3.123
1.101
3.179
3.037
3.181
1.006
0.948
0.982
0.966
0.929
1.050
1.054
1.017
1.045
0.989
1.000
NAME XS-1-136-A1EXPNO 1PROCNO 1Date_ 20111217Time 14.58INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zg30TD 65536SOLVENT C6D6NS 32DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 203DW 60.800 usecDE 6.50 usecTE 294.9 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 7.10 usecPL1 -2.00 dBPL1W 13.17734718 WSFO1 400.1324710 MHzSI 32768SF 400.1300441 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-136-A1EXPNO 4PROCNO 1Date_ 20111223Time 9.32INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT C6D6NS 12972DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 181DW 20.800 usecDE 6.50 usecTE 299.8 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.90 usecPL1 -2.00 dBPL1W 55.33689499 WSFO1 100.6379183 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -1.00 dBPL12 15.16 dBPL13 18.62 dBPL2W 13.56617069 WPL12W 0.32844096 WPL13W 0.14806664 WSFO2 400.1916008 MHzSI 32768SF 100.6278192 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
15.397
15.478
20.072
20.973
45.019
51.943
56.366
62.573
69.842
76.578
84.003
95.778
119.114
127.331
127.818
128.059
128.300
128.680
135.563
139.748
168.641
Bruker Advance III 400
69
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm1.0083
1.1590
2.7473
2.7518
2.7709
2.7755
1.4225
1.5567
2.0285
2.0464
2.5487
2.5662
4.8865
4.8953
4.9039
4.9128
5.0860
5.0941
5.1490
5.1737
5.1957
5.4851
5.5095
5.5274
5.5342
5.5518
5.5767
5.8807
5.9046
6.6713
6.6761
6.6951
6.7001
6.9778
6.9962
7.0145
7.0327
7.2600
3.045
3.062
3.025
3.019
1.039
1.041
1.062
0.966
2.058
1.106
1.018
1.123
1.000
NAME XS-1-138-A1EXPNO 21PROCNO 1Date_ 20120213Time 13.39INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 32DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 161DW 60.800 usecDE 6.50 usecTE 297.6 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 14.00 usecPL1 -1.00 dBPL1W 13.56617069 WSFO1 400.1924713 MHzSI 32768SF 400.1900141 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
Bruker Advance III 400
NAME XS-1-138-A1EXPNO 22PROCNO 1Date_ 20120229Time 21.18INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 12822DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 298.9 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 9.90 usecPL1 -2.00 dBPL1W 55.33689499 WSFO1 100.6379183 MHz
======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -1.00 dBPL12 15.16 dBPL13 18.62 dBPL2W 13.56617069 WPL12W 0.32844096 WPL13W 0.14806664 WSFO2 400.1916008 MHzSI 32768SF 100.6278416 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
12.842
16.179
19.782
22.498
47.026
60.620
62.794
64.033
76.842
77.160
77.477
77.765
83.802
94.507
121.734
126.970
127.684
132.374
141.886
157.123
169.529
201.605
Bruker Advance III 400
70
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012