carbonyls with diselenides electrochemical …solution) as the anode and platinum plate (1.5 cm ×...
TRANSCRIPT
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Electrochemical Oxidative Cyclization of Olefinic
Carbonyls with DiselenidesZhipeng Guan,a Yunkun Wang,a Huamin Wang,a Yange Huang,a Siyuan Wang,a Hongding Tang*,
a Heng Zhang*,a Aiwen Lei*,a
a Engineering Research Center of Organosilicon Compounds & Materials, Ministry of Education,
College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, 430072, P.R. China
*Email: [email protected]
Supporting Information
Electronic Supplementary Material (ESI) for Green Chemistry.This journal is © The Royal Society of Chemistry 2019
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Table of ContentsGeneral information………………………….…………………………….…...S3
Experimental section…………………….……………………………………...S3
1) General procedure for preparation of olefinic carbonyl compounds.………..S32) General procedure for preparation electrochemical oxidative cyclization of
olefinic carbonyls with diselenides……………...……………….……………..S4
3) Gram-scale experiments…………………….……….…………………….…...S54) Control experiment………………….………………….……...…….……..…..S55) Derivatization of products ……….………….……...…………………..……...S56) Procedure for cyclic voltammetry (CV) ……….………….……...……..……..S6
Detail descriptions for
products……………….………….…………………..S7
References……………….…………..….……….……….………………..……..S17
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General informationAll glassware was oven dried at 110 ℃ for hours and cooled down under vacuum. Unless otherwise noted, all reagents were purchased from commercial suppliers and used without further purification. The instrument for electrolysis was dual display potentiostat (DJS-292B) (made in China). Cyclic voltammograms were obtained on a CHI 605E potentiostat. The anodic electrode was graphite rod (ϕ 6 mm, hard) and cathodic electrode was platinum sheet (1.5 cm×1.5 cm×0.3 mm). These electrodes were commercially available from GaossUnion, China. Thin layer chromatography (TLC) employed glass 0.25 mm silica gel plates. Flash chromatography columns were packed with 200-300 mesh silica gel in petroleum (bp. 60-90 ℃). GC-MS spectra were recorded on a Varian GC-MS 3900-2100T. The known compounds were characterized by 1H NMR, 13C NMR and 19F NMR. 1H, 19F and 13C NMR data were recorded with ADVANCE III 400 MHz with tetramethylsilane as an internal standard. High resolution mass spectra (HRMS) were measured with a Waters Micromass GCT instrument. All chemical shifts (δ) were reported in ppm and coupling constants (J) in Hz. All chemical shifts were reported relative to tetramethylsilane (0 ppm for 1H), Chloroform-d (77.16 ppm for 13C), respectively.
Experimental Section1) General procedure for preparation of olefinic carbonyl compounds
Preparation of (3-bromoprop-1-en-2-yl)benzene1. To a solution of α-methylstyrene (20 mmol) in THF (30 mL) was added N-bromosuccinimide (NBS, 25 mmol) and TsOH (2 mmol), and the mixture was heated to reflux for 8 h. After cooling the reaction mixture to room temperature, then quenched with water (100 mL), extracted with EtOAc (3 × 30 mL). The combined organic layer was dried over Na2SO4, filtered and concentrated under reduced pressure to afford the crude product, which was purified by flash column chromatography (PE/EA) to give (3-bromoprop-1-en-2-yl)benzene S1.
Ph Ph
Br+ NBS
TSOH, THF
reflux
S1
Preparation of 1a-1l, 1p1. The substituted acetophenones (10 mmol) was dissolved in THF (30 mL) in a dried round bottom flask under an N2 atmosphere. The solution was cool down to -78 °C, followed by addition of lithium bis(trimethylsilyl)amide (LiHDMS) (20 mL, 1 M in THF). This solution was stirred at -78 °C for 1 h before the corresponding benzoyl chloride (10 mmol, 1.0 equiv) was added dropwise. The mixture was allowed to warm to room temperature stirred overnight. Then quenched with 1 M HCl (30 mL, 1 M) and water (100 mL), extracted with EtOAc (3 × 50 mL). The combined organic layer was dried over Na2SO4, filtered and concentrated under reduced pressure to afford the crude product, which was purified by flash column chromatography (PE/EA) to give the corresponding products S2.The obtained S2 (10 mmol) was dissolved in DMF (20 mL) in a dried round bottom flask, followed by addition of the corresponding allyl bromide S1 (11 mmol) and K2CO3 (2.07 g, 15mmol). The mixture was stirred at 65 °C for 6 h under an N2 atmosphere. Then diluted with Water (70 mL).
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extracted with EtOAc (3 × 50 mL). The combined organic layer was dried over Na2SO4, filtered and concentrated under reduced pressure to afford the crude product, which was purified by flash column chromatography (PE/EA) to give the corresponding product 1.
O
Me
R1
+
O
Cl
R1
LiHMDS
O
R1
O
R1
Br
R2
K2CO3, DMF, 65℃
R3
R4
O
R1 O
R2R4
R3
R1
THF, -78℃
S2 1
Preparation of 1m-1o, 1q-1v2. To a solution of NaH (12 mmol, 1.2 equiv) in THF (20 mL) at 0 °C was added corresponding olefinic carbonyl compounds (10 mmol, 1.0 equiv) in THF (10 mL) dropwisely, and the mixture was stirred at 0 °C for 1 h. The corresponding allyl bromide S1 (12 mmol, 1.2 equiv) was added to the solution over 5 min and the reaction mixture was further stirred overnight at room temperature. The reaction was quenched with saturated NH4Cl and extracted with ethyl acetate. The combined organic layer was dried over Na2SO4, filtered and concentrated under reduced pressure to afford the crude product, which was purified by flash column chromatography (PE/EA) to give the corresponding products 1.
R
O
EWG R
O
+ Br
EWG
NaH, THF
rt, overnight
1
Preparation of 4a-4q3. To a solution of benzoyl chloride (1.45 mL, 12.5 mmol) in DCM (20 mL) was added dropwise a solotion of allylamine (0.75 mL, 10 mmol) and Et3N (1.39 mL, 10 mmol) in DCM (20 mL) at 0 °C. After the addition, the reaction was allowed to warm to room temperature and stirred overnight. The reaction was quenched with water and the aqueous layer was washed with DCM. The organic layers were combined and evaporated under vacuum. The residue was purified by a flash chromatograph (PE/EA) on silica gel to give desired products 4.
R
O
Cl+ NH2
R
O
NH
Et3N, DCM
rt, overnight
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2) General procedure for preparation electrochemical oxidative cyclization of olefinic carbonyls with diselenides
R1
R2
+ PhSeSePhOR1
R2 SePh
C Pt
O
In an oven-dried undivided three-necked bottle (25 mL) equipped with a stir bar, olefinic carbonyl compounds 1 (0.3 mmol), diselenides 2 (0.3 mmol), and nBu4NBF4 (0.1 mmol) were combined and added. The bottle was equipped with graphite rod (ϕ 6 mm, about 18 mm immersion depth in solution) as the anode and platinum plate (1.5 cm × 1.5 cm × 1 mm) as the cathode and was then charged with nitrogen. Under the protection of N2, HOAc (0.1 mL), MeCN (12.0 mL) were injected respectively into the tubes via syringes. The reaction mixture was stirred and electrolyzed at a
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constant current of 10 mA at 0℃ for 3 h. When the reaction was finished, the pure product was purified by flash column chromatography (PE/EA) on silica gel.
3) Gram-scale experiments
PhSeSePhPh
O
PhO
nBu4NBF4, (1 mmol), HOAc (1 mL)
MeCN (120 mL), 10 mA, 25 h, 0℃,N2,+
O
SePh
Ph
Ph
O0.75g, 60% yield3 mmol 3 mmol
In an oven-dried undivided three-necked bottle (150 mL) equipped with a stir bar, olefinic carbonyl compounds 1b (3 mmol), diselenides 2 (3 mmol), and nBu4NBF4 (1 mmol) were combined and added. The bottle was equipped with graphite rod (ϕ 6 mm) as the anode and platinum plate (1.5 cm × 1.5 cm × 1 mm) as the cathode and was then charged with nitrogen. Under the protection of N2, HOAc (1 mL), MeCN (120 mL) were injected respectively into the tubes via syringes. The reaction mixture was stirred and electrolyzed at a constant current of 10 mA at 0℃ for 25 h. When the reaction was finished, the pure product was purified by flash column chromatography (PE/EA) on silica gel.
4) Control experiment
Ph
O
PhO
+ PhSeSePhstandard condition
0.6 mmol TEMPO
O
SePh
Ph
O
Ph
3ba only trace1b2a
In an oven-dried undivided three-necked bottle (25 mL) equipped with a stir bar, olefinic carbonyl compounds 1b (0.3 mmol), diselenides 2 (0.3 mmol), TEMPO (0.5 mmol) and nBu4NBF4 (0.1 mmol) were combined and added. The bottle was equipped with graphite rod (ϕ 6 mm, about 18 mm immersion depth in solution) as the anode and platinum plate (1.5 cm × 1.5 cm × 1 mm) as the cathode and was then charged with nitrogen. Under the protection of N2, HOAc (0.1 mL), MeCN (12.0 mL) were injected respectively into the tubes via syringes. The reaction mixture was stirred and electrolyzed at a constant current of 10 mA at 0℃ for 3 h.
5) Derivatization of products
3baDABCO, DCM
OO
Ph Br Br
O
Ph
6, 45 mg, 76% yieldSePh
7, 85 mg, 98% yield
H2O2, THFO
Se
Ph
O
Ph
PhOH2O, NBS
Preparation of 6. To a solution of 3ba (0.1 mmol, 1 equiv), DABCO (0.02 mmol, 0.2 equiv) and 30μL H2O in dichloromethane (AR grade, 2 mL) was added NBS (0.25 mmol, 2.5 equiv) under an N2 atmosphere. The resulting mixture was stirred for 3 h in the absence of light at room temperature. When the reaction was finished, the pure product was purified by flash column chromatography (PE/EA) on silica gel.
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Preparation of 7. A mixture of 3ba (0.2 mmol, 1 equiv) and H2O2 (30% in H2O, 2 equiv) in anhydrous THF (2 mL) was stirred at room temperature until complete consumption of the starting material, as monitored by TLC. After the evaporation of the solvent, the residual crude product was purified by flash chromatography.6) Procedure for cyclic voltammetry (CV)
Cyclic voltammetry was performed in a three-electrode cell connected to a schlenk line under nitrogen at room temperature. The working electrode was a steady glassy carbon disk electrode, the counter electrode a platinum wire. The reference was an Ag/AgCl electrode submerged in saturated aqueous KCl solution, and separated from reaction by a salt bridge. 12 mL of MeCN containing 0.04 M nBu4NBF4 were poured into the electrochemical cell in all experiments. The CV of substrates (2a) were measured at the concentration of 0.01M. The scan rate of 2a is 0.05 V/s, ranging from 0 V to 3.0 V and 0 V to -2.5 V.
0.0 0.5 1.0 1.5 2.0 2.5 3.0-4.0x10-5
0.0
4.0x10-5
8.0x10-5
1.2x10-4
1.6x10-4
PhSeSePh (2a)
Curr
ent /
A
Potential / V(vs Ag/AgCl)
-2.5 -2.0 -1.5 -1.0 -0.5 0.0-1.0x10-4
-8.0x10-5
-6.0x10-5
-4.0x10-5
-2.0x10-5
0.0
2.0x10-5
PhSeSePh (2a)
Curr
ent /
A
7
Detail descriptions for products
O
O SePh
F
F
(4-fluorophenyl)(2-(4-fluorophenyl)-5-((phenylselanyl)methyl)-4,5-dihydrofuran-3-yl)methanone (3aa). colorless oil was obtained in 90% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.61 – 7.54 (m, 2H), 7.47 (m, 2H), 7.31 – 7.22 (m, 3H), 7.15 – 7.07 (m, 2H), 6.77 (dt, J = 12.7, 8.6 Hz, 4H), 5.01 (m, 1H), 3.44 (dd, J = 15.2, 9.9 Hz, 1H), 3.36 (dd, J = 12.7, 5.5 Hz, 1H), 3.22 (dd, J = 12.7, 6.8 Hz, 1H), 3.10 (dd, J = 15.2, 7.4 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 191.51, 165.29 (d, J = 101.4 Hz), 164.06, 162.78 (d, J = 100.6 Hz), 135.08 (d, J = 3.0 Hz), 133.23, 131.50 (d, J = 8.7 Hz), 131.33 (d, J = 8.9 Hz), 129.31, 129.17, 127.50, 125.95 (d, J = 3.3 Hz), 115.02 (d, J = 4.1 Hz), 114.80 (d, J = 4.3 Hz), 111.42, 81.08, 38.62, 32.53. 19F NMR (377 MHz, CDCl3) δ -107.34, -108.58. HRMS (ESI) calculated for C24H19F2O2Se+ [M+H]+ 457.0513 found 457.0506.
O
SePh
Ph
Ph
O
phenyl(2-phenyl-5-((phenylselanyl)methyl)-4,5-dihydrofuran-3-yl)methanone (3ba)4. colorless oil was obtained in 91% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.59 (m, 2H), 7.50 – 7.38 (m, 2H), 7.31 – 7.24 (m, 3H), 7.24 – 7.10 (m, 4H), 7.09 – 6.99 (m, 4H), 5.01 (m, 1H), 3.51 – 3.32 (m, 2H), 3.22 (dd, J = 12.6, 7.1 Hz, 1H), 3.12 (dd, J = 15.2, 7.3 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 193.41, 165.47, 138.97, 133.30, 131.22, 130.06, 129.90, 129.38, 129.32, 129.23, 128.94, 127.70, 127.63, 127.50, 111.70, 81.04, 38.60, 32.62.
O
O SePh
Me
Me
(5-((phenylselanyl)methyl)-2-(p-tolyl)-4,5-dihydrofuran-3-yl)(p-tolyl)methanone (3ca). colorless oil was obtained in 75% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.63 – 7.52 (m, 2H), 7.42 – 7.35 (m, 2H), 7.31 – 7.23 (m, 3H), 7.10 – 7.02 (m, 2H), 6.90 (d, J = 7.9 Hz, 2H), 6.85 (d, J = 7.9 Hz, 2H), 4.97 (m, 1H), 3.48 – 3.34 (m, 2H), 3.20 (dd, J = 12.6, 7.2 Hz, 1H), 3.09 (dd, J = 15.2, 7.3 Hz, 1H), 2.24 (s, 3H), 2.22 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 193.26, 164.73, 141.80, 140.27, 136.36, 133.29, 129.32, 129.15, 128.44, 128.35, 127.47, 127.14, 110.89, 80.74, 38.97, 32.60, 21.52, 21.46. HRMS (ESI) calculated for C26H25O2Se+ [M+H]+ 449.1014 found 449.1007.
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O
O SePh
MeO
OMe
(4-methoxyphenyl)(2-(4-methoxyphenyl)-5-((phenylselanyl)methyl)-4,5-dihydrofuran-3-yl)methanone (3da). colorless oil was obtained in 56% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.65 – 7.58 (m, 2H), 7.57 – 7.50 (m, 2H), 7.34 – 7.27 (m, 3H), 7.23 – 7.15 (m, 2H), 6.70 – 6.59 (m, 4H), 4.99 (m, 1H), 3.77 (s, 3H), 3.75 (s, 3H), 3.51 – 3.37 (m, 2H), 3.24 (dd, J = 12.6, 7.1 Hz, 1H), 3.12 (dd, J = 15.1, 7.3 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 192.30, 163.78, 162.27, 160.88, 133.31, 131.69, 131.31, 131.09, 129.39, 129.34, 127.48, 122.47, 113.19, 113.13, 110.05, 80.52, 55.41, 55.35, 39.21, 32.63. HRMS (ESI) calculated for C26H25O4Se+ [M+H]+ 481.0913 found 481.0905.
O
O SePh
Me
Me
(5-((phenylselanyl)methyl)-2-(m-tolyl)-4,5-dihydrofuran-3-yl)(m-tolyl)methanone (3ea). colorless oil was obtained in 69% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.59 (m, 2H), 7.31 – 7.16 (m, 5H), 7.04 – 6.90 (m, 5H), 6.86 (m, 1H), 5.00 (m, 1H), 3.50 – 3.33 (m, 2H), 3.22 (dd, J = 12.6, 7.2 Hz, 1H), 3.11 (dd, J = 15.2, 7.3 Hz, 1H), 2.10 (s, 3H), 2.06 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 193.69, 165.92, 139.05, 137.26, 137.23, 133.25, 131.73, 130.75, 130.18, 129.89, 129.60, 129.31, 129.28, 127.59, 127.54, 127.48, 126.22, 125.95, 111.91, 8101, 38.42, 32.60, 21.03, 20.99. HRMS (ESI) calculated for C26H25O2Se+ [M+H]+ 449.1014 found 449.1005.
O
SePh
Ph
Ph
O
Me
(5-methyl-2-phenyl-5-((phenylselanyl)methyl)-4,5-dihydrofuran-3-yl)(phenyl)methanone (3fa). colorless oil was obtained in 78% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.60 – 7.53 (m, 2H), 7.47 – 7.41 (m, 2H), 7.27 – 7.21 (m, 3H), 7.21 – 6.95 (m, 8H), 3.46 – 3.27 (m, 3H), 3.18 (d, J = 15.1 Hz, 1H), 1.66 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 193.50, 164.88, 139.12, 132.92, 131.10, 130.63, 130.15, 129.95, 129.36, 129.27, 128.96, 127.66, 127.59, 127.24, 111.86, 87.63, 44.04, 39.23, 26.89. HRMS (ESI) calculated for C25H23O2Se+ [M+H]+ 430.0858 found 430.0853.
O
SePh
Ph
Ph
O
Ph
(2,5-diphenyl-5-((phenylselanyl)methyl)-4,5-dihydrofuran-3-yl)(phenyl)methanone (3ga). white solid was obtained in 71% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.54 – 7.41 (m, 6H), 7.36 (dd, J = 8.4, 6.7 Hz, 2H), 7.32 – 7.25 (m, 1H), 7.18 (m, 7H), 7.04 (td, J = 7.6, 4.7 Hz, 4H), 3.80 –
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3.55 (m, 4H). 13C NMR (101 MHz, CDCl3) δ 193.19, 164.46, 144.24, 138.95, 133.01, 131.21, 130.57, 130.09, 129.86, 129.49, 129.13, 128.99, 128.60, 127.87, 127.70, 127.64, 127.16, 124.93, 112.00, 89.73, 45.10, 41.48. HRMS (ESI) calculated for C30H25O2Se+ [M+H]+ 497.1014 found 497.1009.
O
SePh
Ph
Ph
O
OOEt
ethyl 4-benzoyl-5-phenyl-2-((phenylselanyl)methyl)-2,3-dihydrofuran-2-carboxylate (3ha). colorless oil was obtained in 68% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.69 – 7.56 (m, 2H), 7.51 – 7.43 (m, 2H), 7.31 – 7.23 (m, 4H), 7.19 (dt, J = 8.6, 1.6 Hz, 3H), 7.15 – 7.02 (m, 4H), 4.25 (m, 2H), 3.71 – 3.56 (m, 3H), 3.51 (d, J = 15.7 Hz, 1H), 1.31 (t, J = 7.2 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 193.01, 170.86, 164.63, 138.53, 133.62, 131.48, 130.26, 129.83, 129.57, 129.26, 129.19, 129.01, 127.76, 127.62, 127.56, 111.25, 88.07, 62.23, 42.72, 34.92, 14.18. HRMS (ESI) calculated for C27H25O4Se+ [M+H]+ 493.0913 found 493.0906.
O
SePh
Ph
Ph
O
OOMe
methyl 4-benzoyl-5-phenyl-2-((phenylselanyl)methyl)-2,3-dihydrofuran-2-carboxylate (3ia). colorless oil was obtained in 55% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.64 – 7.55 (m, 2H), 7.49 – 7.40 (m, 2H), 7.23 (m, 4H), 7.19 – 7.11 (m, 3H), 7.11 – 6.99 (m, 4H), 3.74 (s, 3H), 3.66 – 3.52 (m, 3H), 3.46 (d, J = 15.8 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 192.99, 171.38, 164.47, 138.53, 133.69, 131.55, 130.32, 129.71, 129.59, 129.25, 129.23, 129.05, 127.82, 127.67, 127.65, 111.24, 88.09, 53.04, 42.71, 35.00. HRMS (ESI) calculated for C25H23O2Se+ [M+H]+ 435.0858 found 435.0851.
O
SePh
Ph
Ph
O
Me
phenyl(2-phenyl-5-(1-(phenylselanyl)ethyl)-4,5-dihydrofuran-3-yl)methanone (3ja). colorless oil was obtained in 70% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.67 (m, 2H), 7.48 (m, 2H), 7.38 – 7.28 (m, 3H), 7.28 – 7.15 (m, 4H), 7.14 – 7.02 (m, 4H), 5.03 – 4.84 (m, 1H), 3.77 – 3.54 (m, 1H), 3.46 (m, 1H), 3.29 (m, 1H), 1.60 (m, 3H). 13C NMR (101 MHz, CDCl3) δ 193.41, 193.39, 165.78, 165.74, 139.06, 135.73, 135.13, 131.15, 130.03, 130.01, 129.98, 129.95, 129.36, 129.31, 129.23, 129.14, 128.95, 128.93, 128.30, 128.10, 127.98, 127.69, 127.65, 127.60, 112.23, 112.00, 85.22, 84.52, 43.52, 42.65, 37.34, 35.59, 18.07, 16.60. HRMS (ESI) calculated for C25H23O2Se+ [M+H]+ 430.0858 found 430.0851.
O
SePh
Ph
Ph
O
Ph
phenyl(2-phenyl-5-(phenyl(phenylselanyl)methyl)-4,5-dihydrofuran-3-yl)methanone (3ka). colorless oil was obtained in 37% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.47 – 7.41 (m, 2H), 7.36 – 7.16 (m, 11H), 7.16 – 7.07 (m, 3H), 7.06 – 6.96 (m, 4H), 5.31 (ddd, J = 10.2, 7.8, 6.5 Hz, 1H), 4.51 (d, J = 6.5 Hz, 1H), 3.50 (dd, J = 15.3, 10.1 Hz, 1H), 3.27 (dd, J = 15.4, 7.8 Hz, 1H). 13C
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NMR (101 MHz, CDCl3) δ 193.39, 165.36, 138.97, 138.79, 135.77, 131.26, 130.07, 129.81, 129.43, 129.11, 128.96, 128.95, 128.48, 128.41, 128.35, 127.70, 127.64, 127.59, 111.94, 83.39, 52.71, 37.93. HRMS (ESI) calculated for C30H25O2Se+ [M+H]+ 497.1014 found 497.1004.
O
SePh
Ph
Ph
O
MeMe
phenyl(2-phenyl-5-(2-(phenylselanyl)propan-2-yl)-4,5-dihydrofuran-3-yl)methanone (3la). colorless oil was obtained in 26% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.76 – 7.65 (m, 2H), 7.47 – 7.34 (m, 3H), 7.34 – 7.27 (m, 2H), 7.24 – 7.13 (m, 4H), 7.10 – 7.00 (m, 4H), 4.73 (dd, J = 10.0, 9.0 Hz, 1H), 3.38 (dd, J = 9.4, 1.3 Hz, 2H), 1.51 (s, 3H), 1.48 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 193.56, 166.03, 139.19, 138.61, 131.18, 130.11, 130.06, 129.38, 129.06, 129.00, 128.96, 127.75, 127.69, 126.45, 112.39, 88.49, 48.94, 35.47, 26.34, 24.16. HRMS (ESI) calculated for C26H25O2Se+ [M+H]+ 449.1014 found 449.1008.
OPh
Ph
O
SePh
phenyl(2-phenyl-7-(phenylselanyl)-3a,4,5,6,7,7a-hexahydrobenzofuran-3-yl)methanone (3ma). colorless oil was obtained in 52% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.74 – 7.65 (m, 2H), 7.53 – 7.45 (m, 2H), 7.39 – 7.29 (m, 3H), 7.26 – 7.18 (m, 1H), 7.16 – 7.10 (m, 1H), 7.10 – 7.04 (m, 4H), 7.03 – 6.96 (m, 2H), 4.80 (dd, J = 7.4, 5.8 Hz, 1H), 3.76 (ddd, J = 7.9, 5.8, 4.4 Hz, 1H), 3.68 (q, J = 6.9 Hz, 1H), 2.21 – 2.00 (m, 2H), 1.79 (m, 2H), 1.65 – 1.52 (m, 1H), 1.47 (m, 1H). 13C NMR (101 MHz, CDCl3) δ 193.60, 165.48, 138.98, 135.48, 131.53, 130.16, 130.05, 129.54, 129.29, 129.17, 128.61, 128.09, 127.80, 127.67, 117.53, 85.29, 44.20, 43.11, 28.92, 26.37, 21.06. HRMS (ESI) calculated for C27H25O2Se+ [M+H]+ 461.1014 found 461.1006.
O
SePh
Ph
Me
O88% (2.6:1)
O
SePh
Me
Ph
O
+
3na 3na
1-(2-phenyl-5-((phenylselanyl)methyl)-4,5-dihydrofuran-3-yl)ethan-1-one (3na) and (2-methyl-5-((phenylselanyl)methyl)-4,5-dihydrofuran-3-yl)(phenyl)methanone (3n'a). colorless oil was obtained in 88% isolated yield.
3na: 1H NMR (400 MHz, Chloroform-d) δ 7.55 (m, 4H), 7.50 – 7.44 (m, 1H), 7.43 – 7.36 (m, 2H), 7.30 – 7.22 (m, 3H), 4.84 (m, 1H), 3.29 – 3.17 (m, 2H), 3.10 (dd, J = 12.7, 6.9 Hz, 1H), 2.97 – 2.86 (m, 1H), 1.76 (t, J = 1.5 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 193.12, 168.49, 140.85, 133.24, 131.10, 129.29, 129.25, 128.32, 127.83, 127.50, 112.27, 81.31, 36.94, 32.68, 15.52. HRMS (ESI) calculated for C19H19O2Se+ [M+H]+ 359.0545 found 359.0541.3n'a: 1H NMR (400 MHz, Chloroform-d) δ 7.61 – 7.53 (m, 2H), 7.51 – 7.37 (m, 5H), 7.30 – 7.23 (m, 3H), 4.91 (m, 1H), 3.40 – 3.20 (m, 2H), 3.13 (dd, J = 12.6, 7.3 Hz, 1H), 2.95 (dd, J = 15.2, 7.2 Hz, 1H), 1.94 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 194.71, 165.83, 133.39, 130.78, 130.73, 129.36, 129.29, 129.20, 128.41, 127.58, 114.42, 81.23, 37.18, 32.75, 29.07. HRMS (ESI) calculated for C19H19O2Se+ [M+H]+ 359.0545 found 359.0541.
11
O
SePh
Ph
NC
2-phenyl-5-((phenylselanyl)methyl)-4,5-dihydrofuran-3-carbonitrile (3oa)4. colorless oil was obtained in 76% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.92 – 7.83 (m, 2H), 7.64 – 7.57 (m, 2H), 7.52 – 7.40 (m, 3H), 7.36 – 7.26 (m, 3H), 5.03 (m, 1H), 3.34 (dd, J = 12.8, 5.4 Hz, 1H), 3.25 (dd, J = 14.9, 10.1 Hz, 1H), 3.14 (dd, J = 12.8, 7.4 Hz, 1H), 2.92 (dd, J = 14.8, 7.3 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 166.48, 133.48, 131.40, 129.38, 128.66, 128.63, 127.81, 127.73, 127.07, 117.65, 82.13, 79.00, 37.16, 32.08.
O
SePh
Ph
Ts
5-phenyl-2-((phenylselanyl)methyl)-4-tosyl-2,3-dihydrofuran (3pa). colorless oil was obtained in 50% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.64 – 7.55 (m, 4H), 7.50 – 7.45 (m, 2H), 7.45 – 7.41 (m, 1H), 7.40 – 7.32 (m, 2H), 7.29 – 7.20 (m, 5H), 4.87 (m, 1H), 3.34 – 3.16 (m, 2H), 3.05 (dd, J = 12.7, 7.4 Hz, 1H), 2.94 (dd, J = 14.7, 7.2 Hz, 1H), 2.39 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 163.10, 143.78, 138.89, 133.38, 130.98, 129.67, 129.55, 129.36, 128.79, 128.42, 127.82, 127.65, 127.10, 110.32, 80.60, 37.75, 32.34, 21.67. HRMS (ESI) calculated for C24H23O3SSe+ [M+H]+ 471.0528 found 457.0514.
O
SePh
Ph
EtO
O
ethyl 2-phenyl-5-((phenylselanyl)methyl)-4,5-dihydrofuran-3-carboxylate (3qa)3. colorless oil was obtained in 65% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.74 – 7.67 (m, 2H), 7.60 – 7.52 (m, 2H), 7.45 – 7.31 (m, 3H), 7.29 – 7.21 (m, 3H), 4.89 (m, 1H), 4.12 (q, J = 7.1 Hz, 2H), 3.39 – 3.20 (m, 2H), 3.10 (dd, J = 12.6, 7.5 Hz, 1H), 2.93 (dd, J = 15.4, 7.1 Hz, 1H), 1.20 (t, J = 7.1 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 165.27, 164.58, 133.34, 130.42, 129.91, 129.39, 129.31, 129.20, 127.65, 127.48, 102.07, 80.51, 59.89, 37.27, 32.65, 14.35.
O
SePh
Me
tBuO
O
tert-butyl 2-methyl-5-((phenylselanyl)methyl)-4,5-dihydrofuran-3-carboxylate (3ra). colorless oil was obtained in 41% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.62 – 7.48 (m, 2H), 7.27 (dd, J = 4.8, 1.8 Hz, 3H), 4.72 (m, 1H), 3.19 (dd, J = 12.5, 5.8 Hz, 1H), 3.07 – 2.87 (m, 2H), 2.63 (m, 1H), 2.10 (m, 3H), 1.47 (s, 9H). 13C NMR (101 MHz, CDCl3) δ 166.23, 165.72, 133.26, 129.28, 127.45, 103.17, 80.72, 79.70, 35.90, 32.86, 28.52, 14.20. HRMS (ESI) calculated for C26H25O2Se+ [M+H]+ 449.1014 found 449.1007. HRMS (ESI) calculated for C17H22O3SeNa+ [M+Na]+ 377.0626 found 377.0620.
O
SePh
Me
EtO
O
12
ethyl 2-methyl-5-((phenylselanyl)methyl)-4,5-dihydrofuran-3-carboxylate (3sa). colorless oil was obtained in 78% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.59 – 7.49 (m, 2H), 7.26 (m, 3H), 4.76 (m, 1H), 4.16 (q, J = 7.1 Hz, 2H), 3.20 (dd, J = 12.6, 5.7 Hz, 1H), 3.10 – 2.95 (m, 2H), 2.69 (m, 1H), 2.13 (t, J = 1.6 Hz, 3H), 1.27 (t, J = 7.1 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 167.46, 166.12, 133.20, 129.26, 129.24, 127.41, 101.70, 81.00, 59.57, 35.51, 32.76, 14.54, 14.14. HRMS (ESI) calculated for C15H19O3Se+ [M+H]+ 327.0494 found 327.0492.
O
SePh
Me
MeO
O
methyl 2-methyl-5-((phenylselanyl)methyl)-4,5-dihydrofuran-3-carboxylate (3ta)4. colorless oil was obtained in 82% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.61 – 7.49 (m, 2H), 7.33 – 7.19 (m, 3H), 4.76 (m, 1H), 3.69 (s, 3H), 3.19 (dd, J = 12.5, 5.7 Hz, 1H), 3.10 – 2.94 (m, 2H), 2.69 (m, 1H), 2.13 (t, J = 1.6 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 167.84, 166.51, 133.25, 129.29, 129.27, 127.46, 101.48, 81.13, 50.95, 35.50, 32.79, 14.13.
O
SePh
Me
Me
O
1-(2-methyl-5-((phenylselanyl)methyl)-4,5-dihydrofuran-3-yl)ethan-1-one (3ua)4. colorless oil was obtained in xx% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.59 – 7.50 (m, 2H), 7.27 (q, J = 2.7 Hz, 3H), 4.78 (m, 1H), 3.20 (dd, J = 12.6, 5.5 Hz, 1H), 3.14 – 2.99 (m, 2H), 2.82 – 2.69 (m, 1H), 2.17 (s, 3H), 2.15 (t, J = 1.5 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 194.59, 167.31, 133.28, 129.30, 129.18, 127.54, 111.84, 81.15, 36.20, 32.72, 29.57, 15.05.
O
O
SePh
2-((phenylselanyl)methyl)-3,5,6,7-tetrahydrobenzofuran-4(2H)-one (3va). colorless oil was obtained in 93% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.54 (m, 2H), 7.28 (m, 3H), 4.95 (m, 1H), 3.22 (dd, J = 12.7, 5.9 Hz, 1H), 3.08 (dd, J = 12.8, 6.8 Hz, 1H), 3.03 – 2.91 (m, 1H), 2.64 (m, 1H), 2.44 – 2.23 (m, 4H), 2.07 – 1.93 (m, 2H). 13C NMR (101 MHz, CDCl3) δ 195.56, 177.04, 133.35, 129.28, 129.02, 127.58, 112.95, 84.38, 36.45, 32.72, 31.82, 23.89, 21.69. HRMS (ESI) calculated for C15H17O2Se+ [M+H]+ 309.0388 found 309.0386.
O
SeMe
Ph
Ph
O
(5-((methylselanyl)methyl)-2-phenyl-4,5-dihydrofuran-3-yl)(phenyl)methanone (3ab). white solid was obtained in 60% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.48 – 7.42 (m, 2H), 7.25 – 7.14 (m, 4H), 7.11 – 7.01 (m, 4H), 5.07 (m, 1H), 3.46 (dd, J = 15.1, 9.8 Hz, 1H), 3.13 (dd, J = 15.1, 7.7 Hz, 1H), 3.01 (dd, J = 12.7, 5.6 Hz, 1H), 2.92 (dd, J = 12.8, 6.8 Hz, 1H), 2.11 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 193.52, 165.53, 139.04, 131.22, 130.09, 130.03, 129.40, 128.96, 127.72, 127.70, 111.86, 81.87, 38.79, 30.06, 5.35. HRMS (ESI) calculated for C19H19O2Se+ [M+H]+ 359.0545 found 359.0541.
13
O
SeCH2Ph
Ph
Ph
O
(5-((benzylselanyl)methyl)-2-phenyl-4,5-dihydrofuran-3-yl)(phenyl)methanone (3ac). colorless oil was obtained in 50% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.47 – 7.42 (m, 2H), 7.28 (d, J = 4.4 Hz, 4H), 7.24 – 7.13 (m, 5H), 7.06 (m, 4H), 4.96 (m, 1H), 3.88 (s, 2H), 3.39 (dd, J = 15.1, 9.8 Hz, 1H), 3.06 (dd, J = 15.2, 7.7 Hz, 1H), 2.98 – 2.82 (m, 2H). 13C NMR (101 MHz, CDCl3) δ 193.50, 165.46, 139.05, 138.95, 131.25, 130.13, 130.03, 129.44, 129.06, 129.00, 128.70, 127.74, 127.73, 127.04, 111.90, 81.82, 38.80, 28.40, 27.95. HRMS (ESI) calculated for C25H23O2Se+ [M+H]+ 435.0858 found 430.0853.
N
O
SePh
Ph
2-phenyl-5-((phenylselanyl)methyl)-4,5-dihydrooxazole (5aa) 3. colorless oil was obtained in 88% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.90 – 7.78 (m, 2H), 7.56 (dd, J = 6.5, 3.0 Hz, 2H), 7.48 – 7.42 (m, 1H), 7.37 (dd, J = 8.3, 6.7 Hz, 2H), 7.25 (m, J = 3.6 Hz, 3H), 4.87 (m, 1H), 4.14 (dd, J = 15.0, 9.5 Hz, 1H), 3.81 (dd, J = 15.0, 6.9 Hz, 1H), 3.27 (dd, J = 12.7, 5.5 Hz, 1H), 3.03 (dd, J = 12.7, 7.5 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 163.72, 133.40, 131.38, 129.30, 128.95, 128.34, 128.18, 127.65, 127.54, 78.89, 60.28, 31.98.
N
O
SePh
MeO
2-(4-methoxyphenyl)-5-((phenylselanyl)methyl)-4,5-dihydrooxazole (5ba)3. colorless oil was obtained in 82% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.85 – 7.75 (m, 2H), 7.62 – 7.50 (m, 2H), 7.27 (m, 3H), 6.94 – 6.83 (m, 2H), 4.86 (m, 1H), 4.13 (dd, J = 14.8, 9.4 Hz, 1H), 3.84 (s, 3H), 3.79 (dd, J = 14.8, 6.8 Hz, 1H), 3.28 (dd, J = 12.7, 5.5 Hz, 1H), 3.04 (dd, J = 12.7, 7.5 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 163.66, 162.15, 133.47, 129.99, 129.36, 129.06, 127.59, 120.21, 113.75, 78.87, 60.28, 55.48, 32.09.
N
O
SePh
Me
5-((phenylselanyl)methyl)-2-(o-tolyl)-4,5-dihydrooxazole (5ca). colorless oil was obtained in 74% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.69 (dd, J = 7.8, 1.5 Hz, 1H), 7.59 – 7.50 (m, 2H), 7.38 – 7.09 (m, 6H), 4.81 (m, 1H), 4.16 (dd, J = 14.9, 9.5 Hz, 1H), 3.84 (dd, J = 14.9, 6.8 Hz, 1H), 3.26 (dd, J = 12.6, 5.4 Hz, 1H), 3.03 (dd, J = 12.6, 7.5 Hz, 1H), 2.57 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 164.12, 138.80, 133.40, 131.26, 130.61, 129.90, 129.30, 128.96, 127.54, 126.98, 125.59, 77.88, 60.61, 32.04, 21.95. HRMS (ESI) calculated for C17H18NOSe+ [M+H]+ 332.0548 found 332.0544.
14
N
O
SePh
F
2-(4-fluorophenyl)-5-((phenylselanyl)methyl)-4,5-dihydrooxazole (5da)3. colorless oil was obtained in 70% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.83 (dd, J = 8.8, 5.5 Hz, 2H), 7.65 – 7.49 (m, 2H), 7.25 (dd, J = 5.0, 1.8 Hz, 3H), 7.04 (t, J = 8.7 Hz, 2H), 4.88 (m, 1H), 4.13 (dd, J = 14.9, 9.5 Hz, 1H), 3.80 (dd, J = 14.9, 6.9 Hz, 1H), 3.26 (dd, J = 12.8, 5.5 Hz, 1H), 3.04 (dd, J = 12.8, 7.2 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ164.73 (d, J = 251.7 Hz), 162.88, 133.44, 130.47 (d, J = 8.8 Hz), 129.34, 128.96, 127.61, 123.93 (d, J = 3.2 Hz), 115.50 (d, J = 22.0 Hz), 79.16, 60.33, 31.99. 19F NMR (377 MHz, CDCl3) δ -108.11.
N
O
SePh
Br
2-(4-bromophenyl)-5-((phenylselanyl)methyl)-4,5-dihydrooxazole (5ea)3. colorless oil was obtained in 58% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.73 – 7.64 (m, 2H), 7.60 – 7.45 (m, 4H), 7.26 (m, 3H), 4.88 (m, 1H), 4.14 (dd, J = 15.1, 9.5 Hz, 1H), 3.80 (dd, J = 15.1, 6.9 Hz, 1H), 3.26 (dd, J = 12.8, 5.4 Hz, 1H), 3.04 (dd, J = 12.8, 7.3 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 162.99, 133.44, 131.62, 129.74, 129.34, 128.92, 127.62, 126.61, 126.08, 79.22, 60.37, 31.96.
N
O
SePh
Cl
2-(3-chlorophenyl)-5-((phenylselanyl)methyl)-4,5-dihydrooxazole (5fa). colorless oil was obtained in 49% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.79 (t, J = 1.9 Hz, 1H), 7.73 (dt, J = 7.8, 1.4 Hz, 1H), 7.59 – 7.51 (m, 2H), 7.42 (ddd, J = 8.1, 2.2, 1.1 Hz, 1H), 7.34 – 7.18 (m, 4H), 4.90 (m, 1H), 4.15 (dd, J = 15.1, 9.5 Hz, 1H), 3.83 (dd, J = 15.2, 6.9 Hz, 1H), 3.26 (dd, J = 12.8, 5.4 Hz, 1H), 3.06 (dd, J = 12.9, 7.2 Hz, 1H). HRMS (ESI) calculated for C16H15ClNOSe+ [M+H]+ 352.0002 found 351.9999.
N
O
SePh
I
2-(4-iodophenyl)-5-((phenylselanyl)methyl)-4,5-dihydrooxazole (5ga). colorless oil was obtained in 79% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.71 (dd, J = 8.5, 1.8 Hz, 2H), 7.59 – 7.48 (m, 4H), 7.30 – 7.19 (m, 3H), 4.87 (m, 1H), 4.12 (dd, J = 15.1, 9.5, 1.6 Hz, 1H), 3.79 (dd, J = 15.1, 7.0, 1.2 Hz, 1H), 3.25 (dd, J = 12.8, 5.5, 1.6 Hz, 1H), 3.03 (dd, J = 12.8, 7.3, 1.6 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 163.08, 137.52, 133.37, 129.69, 129.28, 128.87, 127.55, 127.09, 98.46, 79.14, 60.29, 31.90. HRMS (ESI) calculated for C16H15INOSe+ [M+H]+ 433.9358 found 433.9348.
N
O
SePh
F3C
15
5-((phenylselanyl)methyl)-2-(4-(trifluoromethyl)phenyl)-4,5-dihydrooxazole (5ha) 3. colorless oil was obtained in 69% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.94 (d, J = 8.1 Hz, 2H), 7.63 (d, J = 8.2 Hz, 2H), 7.60 – 7.50 (m, 2H), 7.26 (dd, J = 4.9, 1.9 Hz, 3H), 4.93 (m, 1H), 4.18 (dd, J = 15.3, 9.5 Hz, 1H), 3.86 (dd, J = 15.2, 6.9 Hz, 1H), 3.27 (dd, J = 12.8, 5.4 Hz, 1H), 3.07 (dd, J = 12.8, 7.2 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 162.63, 133.49, 132.97 (d, J = 32.7 Hz), 131.03, 129.37, 128.88, 128.60, 127.68, 125.35 (q, J = 3.8 Hz), 123.87 (d, J = 272.5 Hz), 79.39, 60.42, 31.94. 19F NMR (377 MHz, CDCl3) δ -62.90.
N
O
SePh
2-(naphthalen-2-yl)-5-((phenylselanyl)methyl)-4,5-dihydrooxazole (5ia)3. colorless oil was obtained in 65% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 8.28 (s, 1H), 7.96 (dd, J = 8.6, 1.7 Hz, 1H), 7.84 (m, 3H), 7.67 – 7.41 (m, 4H), 7.37 – 7.16 (m, 3H), 4.94 (m, 1H), 4.21 (dd, J = 15.0, 9.5 Hz, 1H), 3.87 (dd, J = 15.0, 6.9 Hz, 1H), 3.32 (dd, J = 12.8, 5.4 Hz, 1H), 3.09 (dd, J = 12.8, 7.3 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 163.94, 134.76, 133.45, 132.67, 129.34, 129.02, 128.99, 128.78, 128.17, 127.85, 127.62, 127.60, 126.61, 124.94, 124.76, 79.14, 60.44, 32.07.
N
O
SePh
Ph Me
5-methyl-2-phenyl-5-((phenylselanyl)methyl)-4,5-dihydrooxazole (5ja). colorless oil was obtained in 69% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.84 – 7.78 (m, 2H), 7.56 – 7.50 (m, 2H), 7.47 – 7.40 (m, 1H), 7.39 – 7.31 (m, 2H), 7.24 – 7.16 (m, 3H), 4.01 (d, J = 14.8 Hz, 1H), 3.79 (d, J = 14.8 Hz, 1H), 3.27 (s, 2H), 1.57 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 163.07, 133.10, 131.28, 130.39, 129.20, 128.29, 128.16, 127.92, 127.26, 85.89, 65.61, 38.47, 26.05. HRMS (ESI) calculated for C17H18NOSe+ [M+H]+ 322.0548 found 322.0543.
N
O
SePh
S
5-((phenylselanyl)methyl)-2-(thiophen-2-yl)-4,5-dihydrooxazole (5ka)3. colorless oil was obtained in 72% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.62 – 7.52 (m, 2H), 7.48 (dd, J = 3.7, 1.2 Hz, 1H), 7.42 (dd, J = 5.0, 1.2 Hz, 1H), 7.32 – 7.19 (m, 3H), 7.04 (dd, J = 5.0, 3.7 Hz, 1H), 4.96 – 4.78 (m, 1H), 4.13 (dd, J = 14.9, 9.4 Hz, 1H), 3.79 (dd, J = 14.9, 6.8 Hz, 1H), 3.27 (dd, J = 12.7, 5.3 Hz, 1H), 3.03 (dd, J = 12.7, 7.8 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 159.55, 133.43, 130.32, 130.30, 129.92, 129.31, 128.81, 127.60, 79.45, 60.29, 31.76.
N
O
SePh
N
5-((phenylselanyl)methyl)-2-(pyridin-4-yl)-4,5-dihydrooxazole (5la). colorless oil was obtained in 49% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 8.74 – 8.60 (m, 2H), 7.68 – 7.61 (m, 2H), 7.60 – 7.53 (m, 2H), 7.27 (m, 3H), 4.94 (m, 1H), 4.19 (dd, J = 15.4, 9.6 Hz, 1H), 3.87 (dd, J = 15.5, 7.0 Hz, 1H), 3.26 (dd, J = 12.9, 5.3 Hz, 1H), 3.08 (dd, J = 12.9, 7.2 Hz, 1H). 13C NMR (101 MHz, CDCl3)
16
δ 162.11, 150.28, 134.98, 133.48, 129.37, 128.78, 127.71, 121.91, 79.48, 60.43, 31.83. HRMS (ESI) calculated for C15H15N2OSe+ [M+H]+ 319.0344 found 319.0339.
N
O
SePh
O
2-(furan-2-yl)-5-((phenylselanyl)methyl)-4,5-dihydrooxazole (5ma)3. colorless oil was obtained in 68% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.61 – 7.46 (m, 3H), 7.33 – 7.20 (m, 3H), 6.86 (d, J = 3.4 Hz, 1H), 6.46 (dd, J = 3.5, 1.7 Hz, 1H), 4.85 (m, 1H), 4.15 (dd, J = 15.0, 9.4 Hz, 1H), 3.82 (dd, J = 15.0, 6.9 Hz, 1H), 3.27 (dd, J = 12.7, 5.2 Hz, 1H), 3.02 (dd, J = 12.7, 7.9 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 156.09, 145.27, 142.87, 133.40, 129.30, 128.74, 127.61, 114.39, 111.54, 79.16, 60.10, 31.59.
N
O
SePh
Ph
(E)-5-((phenylselanyl)methyl)-2-styryl-4,5-dihydrooxazole (5na). colorless oil was obtained in 54% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.61 – 7.53 (m, 2H), 7.47 – 7.42 (m, 2H), 7.39 – 7.31 (m, 3H), 7.26 (qd, J = 3.9, 1.7 Hz, 3H), 7.20 (d, J = 16.3 Hz, 1H), 6.57 (d, J = 16.3 Hz, 1H), 4.86 – 4.72 (m, 1H), 4.08 (dd, J = 15.4, 9.4 Hz, 1H), 3.75 (dd, J = 15.3, 6.8 Hz, 1H), 3.24 (dd, J = 12.8, 5.5 Hz, 1H), 3.02 (dd, J = 12.8, 7.3 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 163.61, 140.00, 135.19, 133.36, 129.53, 129.29, 129.03, 128.87, 127.55, 127.53, 115.07, 78.63, 60.31, 31.97. HRMS (ESI) calculated for C18H18NOSe+ [M+H]+ 344.0548 found 344.0544.
N
O
SePh
Me
5-((phenylselanyl)methyl)-2-(prop-1-en-2-yl)-4,5-dihydrooxazole (5oa). colorless oil was obtained in 68% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.60 – 7.50 (m, 2H), 7.26 (dt, J = 4.4, 1.6 Hz, 3H), 5.75 – 5.64 (m, 1H), 5.39 (q, J = 1.6 Hz, 1H), 4.74 (m, 1H), 4.05 (dd, J = 15.2, 9.4 Hz, 1H), 3.72 (dd, J = 15.3, 6.9 Hz, 1H), 3.21 (dd, J = 12.6, 5.3 Hz, 1H), 2.96 (dd, J = 12.6, 7.7 Hz, 1H), 1.98 (t, J = 1.2 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 164.76, 133.38, 132.61, 129.30, 128.97, 127.55, 122.02, 78.62, 60.40, 31.93, 19.29. HRMS (ESI) calculated for C13H16NOSe+ [M+H]+ 282.0392 found 282.0386.
N
O
SePh
Cy
2-cyclohexyl-5-((phenylselanyl)methyl)-4,5-dihydrooxazole (5pa). colorless oil was obtained in 50% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.58 – 7.46 (m, 2H), 7.32 – 7.18 (m, 3H), 4.65 (m, 1H), 3.90 (ddd, J = 14.4, 9.5, 1.2 Hz, 1H), 3.57 (ddd, J = 14.4, 6.6, 1.1 Hz, 1H), 3.14 (dd, J = 12.6, 5.5 Hz, 1H), 2.93 (dd, J = 12.5, 7.4 Hz, 1H), 2.21 (m, 1H), 1.94 – 1.83 (m, 2H), 1.80 – 1.70 (m, 2H), 1.69 – 1.60 (m, 1H), 1.47 – 1.13 (m, 5H). 13C NMR (101 MHz, CDCl3) δ 170.96, 133.31, 129.30, 129.11, 127.50, 78.00, 59.62, 37.47, 32.12, 29.82, 29.79, 25.92, 25.72, 25.71. HRMS (ESI) calculated for C16H22NOSe+ [M+H]+ 324.0861 found 324.0855.
N
O
SePh
17
2-cyclopropyl-5-((phenylselanyl)methyl)-4,5-dihydrooxazole (5qa). colorless oil was obtained in 60% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.60 – 7.49 (m, 2H), 7.31 – 7.18 (m, 3H), 4.64 (m, 1H), 3.89 (dd, J = 14.2, 9.3 Hz, 1H), 3.55 (dd, J = 14.2, 6.7 Hz, 1H), 3.13 (dd, J = 12.6, 5.4 Hz, 1H), 2.93 (dd, J = 12.7, 7.4 Hz, 1H), 1.59 (m, 1H), 0.96 – 0.87 (m, 1H), 0.87 – 0.73 (m, 3H). 13C NMR (101 MHz, CDCl3) δ 168.71, 133.31, 129.30, 129.03, 127.53, 78.40, 59.75, 31.93, 8.76, 6.90, 6.84. HRMS (ESI) calculated for C13H16NOSe+ [M+H]+ 282.0392 found 282.0386.
OO
Ph Br Br
O
Ph
SePh
4,4-dibromo-5-oxo-2,5-diphenyl-1-(phenylselanyl)pentan-2-yl benzoate (6). colorless oil was obtained in 76% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 8.19 (dt, J = 7.3, 1.3 Hz, 2H), 7.90 – 7.74 (m, 2H), 7.56 – 7.38 (m, 4H), 7.30 (dt, J = 13.5, 7.8 Hz, 4H), 7.19 – 7.01 (m, 3H), 5.68 (m, 1H), 3.49 – 3.22 (m, 4H). 13C NMR (101 MHz, CDCl3) δ 188.12, 165.61, 133.53, 133.12, 132.97, 132.03, 131.27, 129.91, 129.88, 129.52, 129.24, 128.33, 128.03, 127.29, 72.24, 61.43, 50.10, 32.42. HRMS (ESI) calculated for C20H24Br2O3SeNa+ [M+Na]+ 618.8837 found 616.8837.
O
Se
Ph
O
Ph
PhO
phenyl(2-phenyl-5-((phenylseleninyl)methyl)-4,5-dihydrofuran-3-yl)methanone (7). white solid. was obtained in 98% isolated yield. 1H NMR (400 MHz, Chloroform-d) δ 7.90 – 7.80 (m, 1H), 7.76 (dd, J = 6.5, 2.9 Hz, 1H), 7.60 – 7.49 (m, 3H), 7.48 – 7.41 (m, 2H), 7.28 – 7.15 (m, 3H), 7.15 – 7.00 (m, 5H), 5.44 (m, 0.5H), 5.04 (m, 0.5H), 3.46 (m, 2H), 3.27 – 2.95 (m, 2H). 13C NMR (101 MHz, CDCl3) δ 193.15, 193.12, 164.46, 164.20, 140.36, 139.43, 138.44, 131.66, 131.62, 131.55, 130.37, 130.33, 129.91, 129.85, 129.44, 129.36, 129.32, 129.20, 128.91, 127.80, 127.76, 127.70, 126.24, 125.78, 111.64, 111.36, 76.03, 75.87, 58.95, 57.55, 39.03, 38.93. HRMS (ESI) calculated for C24H21O3Se+ [M+H]+ 437.0650 found 4370632.References(1) Yang, N. Y.; Li, Z. L.; Ye, L.; Tan, B.; Liu, X. Y. Organic base-catalysed solvent-tuned
chemoselective carbotrifluoromethylation and oxytrifluoromethylation of unactivated alkenes. Chem. Commun. 2016, 52, 9052—9055.
(2) Jiang, Y.; Park, C. M.; Loh, T. P. Transition-Metal-Free Synthesis of Substituted Pyridines via Ring Expansion of 2-Allyl-2H-azirines. Org. Lett. 2014, 16, 3432-3435.
(3) Zhang, Q. B.; Yuan, P. F.; Kai, L. L.; Liu, K.; Ban, Y. L.; Wang, X. Y.; Wu, L. Z.; Liu, Q. Preparation of Heterocycles via Visible-Light-Driven Aerobic Selenation of Olefins with Diselenides. Org. Lett. 2019, 21, 4885-889.
(4) Tiecco, M.; Testaferri, L.; Tingoli, M.; Bartoli, D.; Balducci, R. Ring-closure reactions initiated by the peroxydisulfate ion oxidation of diphenyl diselenide. J. Org. Chem. 1990, 55, 429-434.
18
3aa
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
1.03
1.03
2.02
1.00
4.01
2.01
3.05
2.02
1.99
3.07
3.09
3.11
3.13
3.20
3.22
3.23
3.25
3.34
3.35
3.37
3.38
3.41
3.43
3.44
3.47
4.98
4.99
4.99
5.00
5.01
5.01
5.01
5.02
5.02
5.03
5.04
5.05
6.74
6.76
6.77
6.77
6.78
6.79
6.81
7.10
7.11
7.12
7.14
7.26
7.27
7.27
7.27
7.28
7.45
7.46
7.47
7.49
7.56
7.57
7.57
7.58
7.58
7.58
7.59
O
O SePh
F
F
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
32.5
3
38.6
2
76.8
477
.16
77.4
881
.08
111.
4211
4.78
114.
8211
5.00
115.
0412
5.94
125.
9712
7.50
129.
1712
9.31
131.
2913
1.38
131.
4513
1.54
133.
2313
5.07
135.
1016
2.28
163.
2816
4.06
164.
7916
5.79
191.
51
19
-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10010
f1 (ppm)
-108
.58
-107
.34
20
3ba
-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5
f1 (ppm)
1.09
1.03
2.02
1.01
4.20
4.38
2.96
1.94
1.91
3.09
3.11
3.13
3.15
3.19
3.21
3.22
3.24
3.36
3.37
3.39
3.41
3.42
3.45
3.46
3.49
4.99
5.00
5.01
5.01
7.00
7.00
7.02
7.02
7.03
7.04
7.04
7.04
7.06
7.07
7.08
7.11
7.11
7.12
7.13
7.13
7.13
7.14
7.14
7.15
7.15
7.16
7.17
7.18
7.19
7.19
7.20
7.21
7.21
7.22
7.23
7.25
7.25
7.26
7.26
7.27
7.27
7.28
7.28
7.42
7.43
7.43
7.44
7.44
7.45
7.57
7.58
7.58
7.59
7.59
7.60
7.60
O
SePh
Ph
Ph
O
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
32.6
2
38.6
0
76.8
477
.16
77.4
881
.04
111.
7012
7.50
127.
6312
7.70
128.
9412
9.23
129.
3212
9.38
129.
9013
0.06
131.
2213
3.30
138.
97
165.
47
193.
41
21
3ca
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
5.95
1.00
0.99
2.01
1.00
2.00
1.97
1.97
3.02
1.96
1.96
2.22
2.24
3.06
3.08
3.10
3.12
3.17
3.19
3.20
3.22
3.36
3.37
3.39
3.40
3.40
3.42
3.43
3.46
4.95
4.95
4.96
4.96
4.97
4.97
4.98
6.84
6.86
6.89
6.91
7.05
7.05
7.06
7.07
7.25
7.25
7.26
7.26
7.26
7.27
7.28
7.28
7.28
7.38
7.38
7.39
7.40
7.56
7.57
7.57
7.57
7.58
7.58
7.58
7.59
7.59
7.59
O
O SePh
Me
Me
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
21.4
621
.52
32.6
0
38.9
7
76.8
477
.16
77.4
880
.74
110.
89
127.
1412
7.47
128.
3512
8.44
129.
1512
9.32
133.
2913
6.36
140.
2714
1.80
164.
73
193.
26
22
3da
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0
f1 (ppm)
1.01
1.03
2.00
2.91
2.86
1.00
3.92
1.94
3.09
1.96
2.00
3.09
3.11
3.13
3.14
3.21
3.23
3.24
3.26
3.39
3.41
3.43
3.43
3.44
3.45
3.46
3.49
3.75
3.77
4.95
4.97
4.97
4.98
4.98
4.99
4.99
4.99
5.00
5.01
5.01
5.03
6.61
6.62
6.63
6.64
6.64
6.65
6.66
6.67
6.67
7.17
7.17
7.18
7.19
7.29
7.30
7.30
7.31
7.31
7.31
7.32
7.32
7.53
7.54
7.55
7.55
7.60
7.61
7.61
7.62
7.62
7.62
7.63
7.63
7.63
O
O SePh
OMe
OMe
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
32.6
3
39.2
1
55.3
555
.41
76.8
477
.16
77.4
880
.52
110.
0511
3.13
113.
1912
2.47
127.
4812
9.34
129.
3913
1.09
131.
3113
1.69
133.
31
160.
8816
2.27
163.
78
192.
30
23
3ea
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5
f1 (ppm)
2.97
2.93
1.02
1.00
2.00
1.00
0.98
4.95
5.00
1.95
2.06
2.10
3.08
3.10
3.12
3.14
3.19
3.21
3.22
3.24
3.36
3.37
3.39
3.41
3.41
3.43
3.45
3.47
4.96
4.97
4.98
4.98
4.99
4.99
5.00
5.00
5.01
5.01
5.02
6.86
6.86
6.87
6.94
6.94
6.94
6.95
6.95
6.96
6.98
6.99
7.00
7.00
7.02
7.19
7.19
7.19
7.19
7.20
7.22
7.22
7.23
7.24
7.24
7.24
7.25
7.25
7.26
7.26
7.27
7.27
7.28
7.28
7.28
7.57
7.58
7.58
7.59
7.59
7.59
7.60
7.60
7.60
O
O SePh
Me
Me
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
20.9
921
.03
32.6
0
38.4
2
76.8
477
.16
77.4
881
.01
111.
91
125.
9512
6.22
127.
4812
7.54
127.
5912
9.28
129.
3112
9.60
129.
8913
0.18
130.
7513
1.73
133.
2513
7.23
137.
2613
9.05
165.
92
193.
69
24
3fa
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5
f1 (ppm)
3.00
1.01
3.03
8.00
3.17
2.00
1.98
1.66
3.16
3.20
3.30
3.34
3.34
3.38
3.40
3.43
6.98
6.98
6.99
7.00
7.00
7.02
7.02
7.03
7.04
7.05
7.05
7.06
7.07
7.07
7.08
7.08
7.09
7.10
7.10
7.10
7.11
7.12
7.12
7.13
7.13
7.13
7.14
7.15
7.15
7.16
7.18
7.18
7.18
7.19
7.20
7.20
7.21
7.22
7.22
7.23
7.23
7.23
7.24
7.24
7.24
7.25
7.25
7.43
7.43
7.43
7.45
7.45
7.45
7.55
7.55
7.56
7.56
7.57
7.57
7.57
7.58
7.58
7.58
O
SePh
Ph
Ph
O
Me
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
26.8
9
39.2
3
44.0
4
76.8
477
.16
77.4
8
87.6
3
111.
8612
7.24
127.
5912
7.66
128.
9612
9.27
129.
3612
9.95
130.
1513
0.63
131.
1013
2.92
139.
12
164.
88
193.
50
25
3ga
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
4.00
4.07
7.02
1.09
2.09
6.01
3.58
3.61
3.63
3.65
3.66
3.69
3.73
3.77
7.02
7.02
7.03
7.04
7.05
7.06
7.07
7.07
7.13
7.13
7.14
7.14
7.15
7.15
7.16
7.16
7.17
7.17
7.18
7.18
7.19
7.19
7.20
7.20
7.21
7.21
7.22
7.22
7.27
7.27
7.27
7.28
7.29
7.29
7.30
7.31
7.31
7.34
7.35
7.36
7.36
7.38
7.38
7.39
7.42
7.42
7.43
7.43
7.44
7.45
7.45
7.46
7.46
7.47
7.48
7.48
7.48
7.49
7.50
7.50
O
SePh
Ph
Ph
O
Ph
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
41.4
845
.10
76.8
477
.16
77.4
8
89.7
3
112.
00
124.
9312
7.16
127.
6412
7.70
127.
8712
8.60
128.
9912
9.13
129.
4912
9.86
130.
0913
0.57
131.
2113
3.01
138.
9514
4.24
164.
46
193.
19
26
3ha
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
3.15
3.99
2.00
3.95
2.90
3.96
2.04
2.00
1.30
1.31
1.33
3.49
3.53
3.59
3.62
3.62
3.65
3.66
3.68
4.19
4.21
4.21
4.22
4.23
4.24
4.25
4.26
4.27
4.27
4.28
4.29
4.31
7.04
7.04
7.06
7.06
7.07
7.08
7.08
7.09
7.10
7.12
7.12
7.17
7.17
7.18
7.19
7.20
7.20
7.20
7.22
7.22
7.24
7.24
7.24
7.25
7.26
7.26
7.26
7.27
7.27
7.28
7.28
7.29
7.46
7.47
7.47
7.48
7.49
7.49
7.49
7.61
7.61
7.62
7.62
7.62
7.63
7.64
O
SePh
Ph
Ph
O
O
OEt
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
14.1
8
34.9
2
42.7
2
62.2
3
76.8
477
.16
77.4
8
88.0
7
111.
2512
7.56
127.
6212
7.76
129.
0112
9.19
129.
2612
9.57
129.
8313
0.26
131.
4813
3.62
138.
53
164.
63
170.
86
193.
01
27
3ia
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5
f1 (ppm)
1.00
2.93
2.81
3.90
2.88
3.91
1.98
1.95
3.44
3.48
3.54
3.58
3.61
3.61
3.64
3.65
3.74
7.01
7.01
7.02
7.03
7.04
7.04
7.05
7.06
7.07
7.09
7.09
7.12
7.13
7.13
7.14
7.14
7.15
7.15
7.15
7.16
7.17
7.19
7.21
7.21
7.21
7.22
7.22
7.23
7.24
7.24
7.25
7.25
7.26
7.43
7.43
7.44
7.45
7.45
7.45
7.58
7.58
7.58
7.58
7.59
7.59
7.60
O
SePh
Ph
Ph
O
O
OMe
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
35.0
0
42.7
1
53.0
4
76.8
477
.16
77.4
8
88.0
9
111.
2412
7.65
127.
6712
7.82
129.
0512
9.23
129.
2512
9.59
129.
7113
0.32
131.
5513
3.69
138.
53
164.
47
171.
38
192.
99
28
3ja
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
3.06
1.03
1.03
1.02
1.00
4.08
4.08
3.08
2.03
1.97
1.57
1.59
1.60
1.62
3.24
3.26
3.28
3.30
3.45
3.47
3.48
3.51
3.58
3.59
3.61
7.04
7.04
7.06
7.06
7.08
7.08
7.08
7.09
7.09
7.10
7.12
7.12
7.16
7.17
7.17
7.17
7.18
7.19
7.19
7.19
7.20
7.20
7.21
7.21
7.23
7.23
7.25
7.25
7.25
7.27
7.29
7.30
7.31
7.32
7.32
7.33
7.33
7.34
7.34
7.35
7.35
7.47
7.47
7.47
7.48
7.48
7.49
7.49
7.49
7.50
7.66
7.66
7.67
7.67
7.68
7.68
7.69
O
SePh
Ph
Ph
O
Me
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
16.6
018
.07
35.5
937
.34
42.6
543
.52
76.8
477
.16
77.4
884
.52
85.2
2
112.
0011
2.23
127.
6012
7.65
127.
6912
7.98
128.
1012
8.30
128.
9312
8.95
129.
1412
9.23
129.
3112
9.36
129.
9512
9.98
130.
0113
0.03
131.
1513
5.13
135.
7313
9.06
165.
7416
5.78
193.
3919
3.41
29
3ka
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
1.00
0.96
0.94
1.00
3.84
3.06
11.28
2.01
3.24
3.26
3.28
3.30
3.47
3.49
3.51
3.53
4.51
4.52
5.30
5.31
5.31
5.32
5.33
5.33
6.98
6.98
7.00
7.02
7.04
7.05
7.05
7.08
7.08
7.09
7.09
7.10
7.10
7.11
7.12
7.12
7.13
7.13
7.14
7.15
7.18
7.18
7.18
7.20
7.20
7.21
7.21
7.22
7.23
7.23
7.24
7.24
7.25
7.25
7.25
7.26
7.27
7.27
7.28
7.28
7.29
7.29
7.30
7.30
7.32
7.32
7.33
7.33
7.34
7.34
7.43
7.43
7.44
7.45
7.45
7.45
O
SePh
Ph
Ph
O
Ph
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
37.9
3
52.7
1
76.8
477
.16
77.4
883
.39
111.
94
127.
5912
7.64
127.
7012
8.35
128.
4112
8.48
128.
9512
8.96
129.
1112
9.43
129.
8113
0.07
131.
2613
5.77
138.
7913
8.97
165.
36
193.
39
30
3la
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
2.84
2.97
2.00
1.00
3.98
3.99
1.97
3.03
1.94
1.48
1.51
3.37
3.37
3.39
3.39
4.70
4.72
4.73
4.75
7.02
7.02
7.03
7.03
7.03
7.04
7.04
7.05
7.05
7.06
7.06
7.08
7.08
7.14
7.15
7.16
7.16
7.17
7.18
7.18
7.19
7.19
7.20
7.21
7.21
7.22
7.23
7.23
7.23
7.26
7.28
7.28
7.29
7.30
7.30
7.30
7.32
7.32
7.32
7.36
7.37
7.37
7.38
7.39
7.39
7.40
7.40
7.41
7.41
7.42
7.42
7.43
7.43
7.44
7.44
7.68
7.68
7.69
7.70
7.70
7.70
O
SePh
Ph
Ph
O
Me
Me
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
24.1
626
.34
35.4
7
48.9
4
76.8
477
.16
77.4
8
88.4
9
112.
3912
6.45
127.
6912
7.75
128.
9612
9.00
129.
0612
9.38
130.
0613
0.11
131.
1813
8.61
139.
19
166.
03
193.
56
31
3ma
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
1.09
1.09
2.47
2.08
1.03
1.02
1.00
2.06
3.96
1.07
1.04
2.98
2.15
1.99
1.43
1.44
1.45
1.46
1.46
1.47
1.48
1.49
1.50
1.54
1.55
1.56
1.57
1.58
1.59
1.59
1.60
1.61
1.62
1.71
1.72
1.73
1.74
1.75
1.75
1.75
1.76
1.77
1.77
1.79
1.79
1.80
1.81
1.82
1.83
1.84
1.85
1.85
1.86
1.87
1.88
2.03
2.04
2.04
2.05
2.05
2.06
2.07
2.08
2.08
2.09
2.10
2.11
2.11
2.12
2.13
3.65
3.67
3.69
3.70
3.74
3.75
3.75
3.76
3.76
3.77
3.77
3.78
4.78
4.80
4.80
4.82
OPh
Ph
O
SePh
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
21.0
626
.37
28.9
2
43.1
144
.20
76.8
477
.16
77.4
8
85.2
9
117.
5312
7.67
127.
8012
8.09
128.
6112
9.17
129.
2912
9.54
130.
0513
0.16
131.
5313
5.48
138.
98
165.
48
193.
60
32
3na
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
3.03
1.02
1.07
2.02
1.00
3.03
1.99
1.05
3.98
1.76
1.76
1.76
2.87
2.88
2.89
2.90
2.91
2.91
2.91
2.93
2.93
2.93
3.08
3.09
3.11
3.13
3.19
3.19
3.21
3.21
3.22
3.22
3.23
3.23
3.25
3.26
4.82
4.82
4.83
4.84
4.84
4.85
4.85
4.86
4.86
4.87
7.25
7.26
7.27
7.27
7.27
7.28
7.28
7.29
7.37
7.38
7.38
7.39
7.40
7.40
7.41
7.41
7.42
7.44
7.45
7.45
7.46
7.47
7.47
7.48
7.48
7.53
7.54
7.54
7.55
7.55
7.56
7.56
7.57
7.57
7.57
O
SePh
Ph
Me
O
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
15.5
2
32.6
836
.94
76.8
477
.16
77.4
881
.31
112.
27
127.
5012
7.83
128.
3212
9.25
129.
2913
1.10
133.
2414
0.85
168.
49
193.
12
33
3n'a
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
2.98
1.05
1.07
2.04
1.00
3.03
4.89
2.09
1.94
2.92
2.94
2.96
2.98
3.10
3.12
3.14
3.15
3.25
3.28
3.29
3.31
3.32
3.32
3.34
4.88
4.89
4.90
4.90
4.91
4.92
4.92
4.93
4.93
4.94
4.95
7.25
7.26
7.27
7.28
7.29
7.38
7.39
7.39
7.41
7.41
7.42
7.44
7.44
7.45
7.46
7.47
7.47
7.48
7.48
7.49
7.49
7.50
7.55
7.56
7.57
7.57
7.58
O
SePh
Me
O
Ph
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
29.0
732
.75
37.1
8
76.8
477
.16
77.4
881
.23
114.
42
127.
5812
8.41
129.
2012
9.29
129.
3613
0.73
130.
7813
3.39
165.
83
194.
71
34
3oa
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5
f1 (ppm)
1.01
0.98
1.03
1.01
1.00
3.05
3.04
2.03
1.98
2.89
2.91
2.93
2.95
3.11
3.13
3.15
3.17
3.22
3.24
3.26
3.28
3.31
3.33
3.35
3.36
4.99
5.01
5.01
5.02
5.03
5.03
5.03
5.04
5.04
5.05
5.06
7.29
7.30
7.30
7.30
7.31
7.31
7.32
7.32
7.33
7.33
7.42
7.42
7.43
7.43
7.44
7.44
7.44
7.44
7.45
7.46
7.46
7.46
7.47
7.47
7.48
7.48
7.49
7.51
7.58
7.59
7.59
7.59
7.60
7.60
7.60
7.61
7.61
7.61
7.61
7.87
7.87
7.88
7.88
7.89
7.89
O
SePh
Ph
CN
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
32.0
8
37.1
6
76.8
477
.16
77.4
879
.00
82.1
3
117.
6512
7.07
127.
7312
7.81
128.
6312
8.66
129.
3813
1.40
133.
48
166.
48
35
3pa
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)2.96
1.02
0.99
1.99
1.00
5.06
2.03
0.91
2.09
3.91
2.39
2.92
2.93
2.95
2.97
3.02
3.04
3.05
3.07
3.18
3.20
3.22
3.23
3.24
3.27
3.28
3.30
4.85
4.86
4.87
4.87
4.87
4.88
4.89
7.21
7.21
7.22
7.22
7.23
7.23
7.24
7.24
7.24
7.25
7.25
7.25
7.26
7.26
7.26
7.34
7.34
7.34
7.35
7.36
7.36
7.37
7.38
7.38
7.38
7.41
7.42
7.42
7.43
7.44
7.44
7.45
7.45
7.46
7.46
7.47
7.47
7.47
7.47
7.48
7.48
7.57
7.57
7.58
7.58
7.59
7.61
7.61
O
SePh
Ph
Ts
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
21.6
7
32.3
4
37.7
5
76.8
477
.16
77.4
880
.60
110.
32
127.
1012
7.65
127.
8212
8.42
128.
7912
9.36
129.
5512
9.67
130.
9813
3.38
138.
8914
3.78
163.
10
36
3qa
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5
f1 (ppm)
3.09
1.03
1.03
2.03
2.03
1.00
3.11
3.02
2.05
1.97
1.18
1.20
1.22
2.91
2.92
2.94
2.96
3.08
3.09
3.11
3.13
3.24
3.27
3.28
3.29
3.31
3.32
3.34
4.10
4.11
4.13
4.15
4.87
4.87
4.88
4.88
4.89
4.89
4.90
7.24
7.24
7.25
7.25
7.25
7.26
7.26
7.27
7.27
7.28
7.32
7.33
7.33
7.34
7.34
7.34
7.35
7.35
7.36
7.36
7.36
7.37
7.37
7.38
7.38
7.39
7.54
7.55
7.55
7.55
7.56
7.56
7.56
7.57
7.57
7.57
7.58
7.69
7.69
7.70
7.70
7.71
7.71
O
SePh
Ph
OEt
O
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
14.3
5
32.6
5
37.2
7
59.8
9
76.8
477
.16
77.4
880
.51
102.
07
127.
4812
7.65
129.
2012
9.31
129.
3912
9.91
130.
4213
3.34
164.
5816
5.27
37
3ra
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
8.98
2.96
1.02
2.01
1.03
1.00
3.10
1.98
1.47
2.10
2.60
2.61
2.61
2.62
2.62
2.63
2.64
2.64
2.65
2.65
2.66
2.66
2.95
2.96
2.96
2.96
2.97
2.98
2.98
2.99
3.00
3.01
3.01
3.02
3.02
3.17
3.19
3.20
3.22
4.68
4.69
4.70
4.70
4.71
4.72
4.72
4.72
4.73
4.74
4.74
4.75
7.25
7.26
7.26
7.27
7.27
7.27
7.28
7.28
7.52
7.52
7.53
7.53
7.54
7.54
7.55
7.55
7.56
O
SePh
Me
O
O
CH3
CH3
CH3
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
14.2
0
28.5
232
.86
35.9
0
76.8
477
.16
77.4
879
.70
80.7
2
103.
17
127.
4512
9.28
133.
26
165.
7216
6.23
38
3sa
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
3.30
3.00
1.02
2.05
1.02
2.01
1.00
3.03
1.99
1.25
1.27
1.29
2.13
2.13
2.13
2.65
2.66
2.66
2.67
2.67
2.68
2.68
2.68
2.69
2.69
2.70
2.70
2.71
2.71
2.72
2.72
2.98
2.99
3.00
3.00
3.01
3.01
3.02
3.02
3.03
3.03
3.03
3.04
3.04
3.06
3.06
3.06
3.17
3.19
3.21
3.22
4.13
4.15
4.16
4.18
4.72
4.73
4.74
4.74
4.75
4.75
4.76
4.76
4.77
4.78
4.78
4.79
7.25
7.25
7.26
7.27
7.27
7.27
7.52
7.53
7.53
7.54
7.54
7.54
7.55
7.55
O
SePh
Me
OEt
O
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
14.1
414
.54
32.7
635
.51
59.5
7
76.8
477
.16
77.4
881
.00
101.
70
127.
4112
9.24
129.
2613
3.20
166.
1216
7.46
39
3ta
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
2.99
1.03
2.05
1.02
3.00
1.00
3.00
1.96
2.12
2.13
2.13
2.66
2.67
2.68
2.68
2.70
2.70
2.72
2.72
2.99
2.99
2.99
3.00
3.00
3.02
3.02
3.02
3.03
3.03
3.04
3.06
3.06
3.17
3.19
3.20
3.22
3.69
4.73
4.74
4.74
4.75
4.76
4.76
4.77
4.77
4.78
4.78
4.79
4.80
7.24
7.25
7.26
7.26
7.27
7.28
7.28
7.28
7.52
7.52
7.53
7.53
7.53
7.54
7.54
7.54
7.55
7.55
O
SePh
Me
O
OMe
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
14.1
3
32.7
935
.50
50.9
5
76.8
477
.16
77.4
881
.13
101.
48
127.
4612
9.27
129.
2913
3.25
166.
5116
7.84
40
3ua
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5
f1 (ppm)
2.96
2.91
1.02
2.07
1.04
1.00
3.06
1.97
2.15
2.15
2.16
2.17
2.71
2.71
2.73
2.73
2.75
2.75
2.76
2.77
3.00
3.02
3.03
3.05
3.05
3.06
3.08
3.08
3.08
3.09
3.09
3.11
3.12
3.18
3.19
3.21
3.22
4.74
4.75
4.76
4.76
4.77
4.77
4.78
4.78
4.79
4.80
4.80
4.81
7.26
7.26
7.27
7.28
7.28
7.53
7.53
7.54
7.54
7.54
7.55
7.55
7.55
7.56
O
SePh
Me
O
Me
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
15.0
5
29.5
732
.72
36.2
0
76.8
477
.16
77.4
881
.15
111.
84
127.
5412
9.18
129.
3013
3.28
167.
31
194.
59
41
3va
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5
f1 (ppm)
2.33
4.05
1.00
1.02
1.03
1.01
1.00
3.00
1.95
1.97
1.98
1.99
2.00
2.01
2.02
2.04
2.31
2.33
2.34
2.35
2.35
2.36
2.37
2.37
2.37
2.61
2.62
2.62
2.63
2.63
2.64
2.65
2.65
2.66
2.66
2.67
2.94
2.94
2.94
2.96
2.97
2.97
2.97
2.98
3.00
3.00
3.05
3.07
3.08
3.10
3.20
3.21
3.23
3.24
4.93
4.93
4.94
4.94
4.95
4.95
4.95
4.96
4.97
4.97
7.26
7.27
7.27
7.27
7.28
7.28
7.29
7.29
7.53
7.53
7.53
7.54
7.54
7.54
7.55
7.55
7.55
O
O
SePh
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
21.6
923
.89
31.8
232
.72
36.4
5
76.8
477
.16
77.4
884
.38
112.
95
127.
5812
9.02
129.
2813
3.35
177.
04
195.
56
42
3ab
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
2.95
1.03
1.00
1.00
1.00
1.00
3.97
3.95
1.95
2.10
2.11
2.13
2.90
2.91
2.93
2.94
2.99
3.00
3.02
3.03
3.10
3.12
3.14
3.15
3.43
3.46
3.47
3.49
5.03
5.04
5.04
5.05
5.05
5.06
5.06
5.06
5.07
5.07
5.07
5.08
5.08
5.09
5.09
7.03
7.03
7.04
7.05
7.05
7.06
7.06
7.07
7.07
7.07
7.09
7.09
7.15
7.15
7.15
7.16
7.17
7.17
7.18
7.19
7.20
7.20
7.20
7.21
7.21
7.21
7.22
7.22
7.23
7.24
7.27
7.43
7.44
7.44
7.45
7.45
7.46
7.46
O
SeMe
Ph
Ph
O
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
5.35
30.0
6
38.7
9
76.8
477
.16
77.4
881
.87
111.
8612
7.70
127.
7212
8.96
129.
4013
0.03
130.
0913
1.22
139.
04
165.
53
193.
52
43
3ac
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
2.03
1.01
1.01
1.98
1.00
4.00
4.95
3.91
2.06
2.84
2.85
2.87
2.89
2.90
2.91
2.93
2.94
3.03
3.05
3.07
3.09
3.36
3.38
3.40
3.42
3.86
3.88
4.94
4.94
4.94
4.96
4.96
4.96
4.96
4.98
4.98
7.02
7.03
7.03
7.04
7.04
7.05
7.05
7.05
7.06
7.06
7.07
7.07
7.08
7.09
7.09
7.14
7.15
7.15
7.16
7.17
7.17
7.17
7.18
7.18
7.19
7.19
7.20
7.20
7.20
7.21
7.22
7.22
7.22
7.23
7.24
7.24
7.25
7.28
7.29
7.42
7.43
7.43
7.44
7.44
7.45
O
Se
Ph
Ph
OPh
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
27.9
528
.40
38.8
0
76.8
477
.16
77.4
881
.82
111.
9012
7.04
127.
7312
7.74
128.
7012
9.00
129.
0612
9.44
130.
0313
0.13
131.
2513
8.95
139.
05
165.
46
193.
50
5aa
44
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5
f1 (ppm)1.05
1.02
1.03
1.03
1.00
3.08
2.03
1.05
2.02
1.96
3.00
3.02
3.04
3.05
3.25
3.26
3.28
3.29
3.79
3.80
3.82
3.84
4.11
4.14
4.15
4.18
4.83
4.85
4.85
4.86
4.86
4.87
4.87
4.88
4.89
4.89
4.91
7.24
7.25
7.25
7.26
7.27
7.35
7.37
7.37
7.39
7.43
7.43
7.43
7.44
7.45
7.46
7.47
7.54
7.55
7.56
7.57
7.84
7.84
7.86
N
O
SePh
Ph
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
31.9
8
60.2
8
76.8
477
.16
77.4
878
.89
127.
5412
7.65
128.
1812
8.34
128.
9512
9.30
131.
3813
3.40
163.
72
45
5ba
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
1.07
1.06
1.43
2.45
1.05
1.00
1.96
3.03
2.03
1.96
3.01
3.03
3.04
3.06
3.26
3.27
3.29
3.30
3.77
3.78
3.80
3.82
3.84
4.10
4.13
4.14
4.16
4.82
4.84
4.84
4.85
4.85
4.86
4.86
4.87
4.88
4.88
4.90
6.87
6.88
6.89
6.89
7.26
7.26
7.27
7.28
7.28
7.55
7.56
7.56
7.56
7.57
7.57
7.57
7.58
7.78
7.79
7.80
7.81
N
O
SePh
OMe
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
32.0
9
55.4
8
60.2
8
76.8
477
.16
77.4
878
.87
113.
75
120.
2112
7.59
129.
0612
9.36
129.
9913
3.47
162.
1516
3.66
46
5ca
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5
f1 (ppm)3.03
1.03
1.02
1.01
1.01
1.00
2.19
3.00
1.18
2.00
1.02
2.57
3.01
3.02
3.04
3.06
3.24
3.25
3.27
3.28
3.81
3.83
3.85
3.86
4.13
4.15
4.17
4.19
4.79
4.80
4.81
4.81
4.83
7.15
7.16
7.17
7.18
7.20
7.21
7.22
7.24
7.25
7.25
7.26
7.26
7.26
7.27
7.29
7.29
7.30
7.31
7.32
7.33
7.54
7.54
7.54
7.55
7.55
7.55
7.56
7.56
7.56
7.68
7.69
7.70
7.71
N
O
SePh
Me
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
21.9
5
32.0
4
60.6
1
76.8
477
.16
77.4
877
.88
125.
5912
6.98
127.
5412
8.96
129.
3012
9.90
130.
6113
1.26
133.
4013
8.80
164.
12
47
5da
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
1.03
1.02
1.03
1.02
1.00
2.02
3.01
1.98
1.98
3.02
3.04
3.05
3.07
3.23
3.25
3.26
3.28
3.78
3.79
3.81
3.83
4.10
4.13
4.14
4.16
4.84
4.85
4.86
4.86
4.87
4.88
4.88
4.88
4.89
4.90
4.90
4.91
7.02
7.04
7.04
7.07
7.24
7.25
7.25
7.25
7.26
7.54
7.54
7.55
7.55
7.56
7.56
7.81
7.82
7.83
7.85
N
O
SePh
F
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
31.9
9
60.3
3
76.8
477
.16
77.4
879
.16
115.
3911
5.61
123.
9212
3.95
127.
6112
8.96
129.
3413
0.42
130.
5113
3.44
162.
8816
3.48
165.
98
48
-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10010
f1 (ppm)
-108
.11
49
5ea
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
1.02
1.01
1.02
1.01
1.00
3.05
4.01
2.01
3.02
3.04
3.05
3.07
3.23
3.25
3.27
3.28
3.78
3.79
3.81
3.83
4.10
4.13
4.14
4.17
4.85
4.86
4.87
4.87
4.88
4.88
4.89
4.89
4.90
4.90
4.91
4.92
7.25
7.25
7.26
7.27
7.27
7.49
7.50
7.51
7.51
7.54
7.54
7.54
7.55
7.55
7.55
7.56
7.56
7.67
7.68
7.69
7.70
N
O
SePh
Br
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
31.9
6
60.3
7
76.8
477
.16
77.4
879
.22
126.
0812
6.61
127.
6212
8.92
129.
3412
9.74
131.
6213
3.44
162.
99
50
5fa
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
1.04
1.03
1.03
1.02
1.00
4.07
0.96
1.97
0.99
0.93
3.04
3.06
3.07
3.09
3.24
3.25
3.27
3.28
3.80
3.82
3.84
3.86
4.13
4.15
4.16
4.19
4.89
4.90
4.91
4.91
4.92
7.25
7.25
7.26
7.26
7.27
7.27
7.28
7.29
7.31
7.33
7.41
7.41
7.42
7.42
7.43
7.43
7.44
7.44
7.55
7.55
7.56
7.56
7.57
7.57
7.72
7.72
7.72
7.74
7.74
7.74
7.78
7.79
7.79
N
O
SePh
Cl
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
31.9
5
60.3
4
76.8
477
.16
77.4
879
.31
126.
3312
7.69
128.
3112
8.87
129.
3512
9.41
129.
6813
1.43
133.
4713
4.40
162.
63
51
5ga
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5
f1 (ppm)
1.04
1.02
1.03
1.01
1.00
3.03
3.98
2.04
3.00
3.01
3.02
3.02
3.03
3.04
3.05
3.06
3.22
3.22
3.23
3.24
3.25
3.25
3.26
3.27
3.27
3.76
3.76
3.78
3.78
3.80
3.80
3.82
3.82
4.09
4.09
4.11
4.12
4.13
4.13
4.15
4.15
4.83
4.84
4.85
4.85
4.85
4.86
4.86
4.87
4.87
4.88
4.88
4.89
4.89
4.90
4.90
4.91
7.24
7.24
7.25
7.25
7.26
7.52
7.53
7.53
7.54
7.54
7.55
7.55
7.55
7.69
7.70
7.71
7.72
7.72
N
O
SePh
I
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
31.9
0
60.2
9
76.8
577
.16
77.1
877
.48
79.1
4
98.4
6
127.
0912
7.55
128.
8712
9.28
129.
6913
3.37
137.
52
163.
08
52
5ha
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
1.03
1.02
1.03
1.02
1.00
3.04
1.99
2.01
2.00
3.05
3.07
3.08
3.10
3.25
3.26
3.28
3.29
3.83
3.85
3.87
3.88
4.15
4.18
4.19
4.21
4.89
4.91
4.91
4.92
4.93
4.93
4.93
4.94
4.94
4.95
4.95
4.97
7.24
7.25
7.25
7.26
7.26
7.27
7.27
7.28
7.54
7.55
7.55
7.56
7.56
7.56
7.57
7.57
7.62
7.64
7.93
7.95
N
O
SePh
CF3
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
31.9
4
60.4
2
76.8
477
.16
77.4
879
.39
119.
8112
2.52
125.
2212
5.29
125.
3312
5.37
125.
4112
7.68
127.
9312
8.60
128.
8812
9.37
131.
0313
2.48
132.
8113
3.13
133.
4413
3.49
162.
63
53
-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10010
f1 (ppm)
-62.
90
54
5ia
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
1.09
1.04
1.03
1.00
0.99
3.00
4.01
3.01
1.05
0.99
3.06
3.08
3.09
3.11
3.30
3.31
3.33
3.34
3.85
3.86
3.88
3.90
4.18
4.20
4.21
4.24
4.92
4.92
4.93
4.93
4.94
4.94
4.95
4.96
7.24
7.24
7.25
7.25
7.26
7.27
7.27
7.48
7.50
7.50
7.51
7.52
7.52
7.53
7.54
7.55
7.55
7.57
7.58
7.58
7.58
7.59
7.60
7.82
7.82
7.84
7.85
7.86
7.87
7.87
7.95
7.96
7.97
7.98
8.28
8.28
N
O
SePh
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
32.0
7
60.4
4
76.8
477
.16
77.4
879
.14
124.
7612
4.94
126.
6112
7.60
127.
6212
7.85
128.
1712
8.78
128.
9912
9.02
129.
3413
2.67
133.
4513
4.76
163.
94
55
5ja
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
2.98
1.83
1.00
1.00
2.89
2.00
1.01
1.96
1.93
1.57
3.27
3.77
3.81
3.99
4.02
7.19
7.19
7.20
7.20
7.20
7.21
7.22
7.23
7.34
7.34
7.34
7.35
7.36
7.36
7.37
7.38
7.42
7.42
7.43
7.44
7.44
7.45
7.46
7.46
7.46
7.51
7.52
7.52
7.53
7.53
7.54
7.54
7.55
7.80
7.80
7.81
7.82
7.82
7.82
N
O
SePh
Ph Me
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
26.0
5
38.4
7
65.6
1
76.8
477
.16
77.4
8
85.8
9
127.
2612
7.92
128.
1612
8.29
129.
2013
0.39
131.
2813
3.10
163.
07
56
5ka
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
1.04
1.02
1.02
1.02
1.00
1.02
3.04
0.96
1.00
1.98
3.00
3.02
3.03
3.04
3.05
3.25
3.26
3.28
3.29
3.77
3.78
3.80
3.82
4.10
4.12
4.13
4.16
4.84
4.84
4.85
4.85
4.86
4.86
4.87
4.87
4.88
4.88
4.88
7.02
7.03
7.04
7.05
7.24
7.25
7.26
7.27
7.28
7.41
7.42
7.42
7.43
7.48
7.48
7.49
7.49
7.54
7.54
7.55
7.55
7.56
7.56
7.57
7.57
N
O
SePh
S
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
31.7
6
60.2
9
76.8
477
.16
77.4
879
.45
127.
6012
8.81
129.
3112
9.92
130.
3013
0.32
133.
43
159.
55
57
5la
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5
f1 (ppm)
1.05
1.02
1.02
1.02
1.00
3.07
1.97
1.97
2.01
3.06
3.07
3.09
3.11
3.24
3.25
3.27
3.29
3.84
3.86
3.88
3.90
4.16
4.18
4.20
4.22
4.90
4.92
4.92
4.93
4.93
4.94
4.94
4.95
4.96
4.96
4.98
7.24
7.25
7.26
7.27
7.27
7.28
7.28
7.54
7.54
7.55
7.55
7.56
7.57
7.64
7.65
7.65
7.66
8.67
8.67
8.68
8.68
N
O
SePh
N
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
31.8
3
60.4
3
76.8
477
.16
77.4
879
.48
121.
9112
7.71
128.
7812
9.37
133.
4813
4.98
150.
28
162.
11
58
5ma
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5
f1 (ppm)
1.01
1.02
1.01
1.02
1.00
0.99
0.97
3.02
3.01
2.99
3.01
3.02
3.04
3.25
3.26
3.28
3.29
3.79
3.81
3.83
3.85
4.12
4.14
4.15
4.18
4.81
4.83
4.83
4.84
4.85
4.85
4.86
4.86
4.87
4.87
4.89
6.45
6.46
6.46
6.46
6.86
6.86
7.25
7.26
7.27
7.27
7.28
7.28
7.52
7.52
7.52
7.54
7.54
7.55
7.55
7.56
7.56
7.56
N
O
SePh
O
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
31.5
9
60.1
0
76.8
477
.16
77.4
879
.16
111.
5411
4.39
127.
6112
8.74
129.
3013
3.40
142.
8714
5.27
156.
09
59
5na
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
0.99
1.00
1.02
1.00
1.00
1.00
1.04
2.97
2.94
2.00
1.98
3.00
3.01
3.03
3.05
3.22
3.23
3.24
3.25
3.26
3.72
3.74
3.76
3.78
4.05
4.08
4.09
4.12
4.76
4.77
4.78
4.78
4.79
4.80
4.80
4.81
4.82
4.82
4.83
6.55
6.59
7.18
7.22
7.25
7.26
7.26
7.27
7.33
7.34
7.34
7.35
7.36
7.37
7.43
7.44
7.44
7.45
7.46
7.55
7.56
7.57
7.57
7.57
7.58
N
O
SePh
Ph
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
31.9
7
60.3
1
76.8
477
.16
77.4
878
.63
115.
07
127.
5312
7.55
128.
8712
9.03
129.
2912
9.53
133.
3613
5.19
140.
00
163.
61
60
5oa
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5
f1 (ppm)
2.99
1.03
1.03
1.03
1.02
1.00
1.00
1.01
3.03
1.97
1.98
1.98
1.99
2.94
2.96
2.97
2.99
3.19
3.21
3.22
3.24
3.69
3.71
3.73
3.74
4.02
4.05
4.06
4.08
4.70
4.72
4.72
4.72
4.73
4.73
4.74
4.74
4.74
4.75
4.75
4.76
4.76
4.76
4.78
5.38
5.39
5.39
5.39
5.40
5.71
5.71
5.71
5.71
7.25
7.26
7.26
7.27
7.27
7.27
7.54
7.54
7.54
7.55
7.55
7.56
N
O
SePh
CH2
Me
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
19.2
9
31.9
3
60.4
0
76.8
477
.16
77.4
878
.62
122.
0212
7.55
128.
9712
9.30
132.
6113
3.38
164.
76
61
5pa
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
5.09
1.09
2.08
2.03
1.00
1.05
1.02
1.02
1.02
1.00
3.10
2.02
1.21
1.21
1.21
1.22
1.23
1.24
1.24
1.25
1.25
1.27
1.28
1.35
1.36
1.36
1.38
1.38
1.39
1.39
1.73
1.73
1.74
1.74
1.75
1.76
1.76
1.77
1.86
1.86
1.87
1.87
1.89
1.90
1.90
2.21
2.91
2.93
2.94
2.96
3.12
3.13
3.15
3.16
3.55
3.55
3.56
3.57
3.58
3.58
3.60
3.60
3.87
3.87
3.89
3.90
3.91
3.91
3.93
3.93
7.26
7.26
7.27
7.27
7.28
7.28
7.53
7.53
7.53
7.54
7.54
7.54
7.55
7.55
N
O
SePh
Cy
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
25.7
125
.72
25.9
229
.79
29.8
232
.12
37.4
7
59.6
2
76.8
477
.16
77.4
878
.00
127.
5012
9.11
129.
3013
3.31
170.
96
62
5qa
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5
f1 (ppm)
3.18
1.00
0.99
1.06
1.02
1.02
1.02
1.00
3.02
1.96
0.77
0.78
0.79
0.79
0.80
0.80
0.81
0.81
0.82
0.82
0.82
0.83
0.83
0.84
0.84
0.84
0.85
0.89
0.89
0.90
0.90
0.90
0.91
0.92
0.92
0.92
1.57
1.57
1.58
1.59
1.59
1.60
1.61
2.90
2.92
2.93
2.95
3.11
3.13
3.14
3.16
3.52
3.54
3.56
3.58
3.86
3.88
3.90
3.92
4.61
4.62
4.62
4.63
4.64
4.64
4.65
7.26
7.26
7.26
7.27
7.27
7.28
7.28
7.28
7.52
7.52
7.53
7.53
7.53
7.54
7.54
7.54
N
O
SePh
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
6.84
6.90
8.76
31.9
3
59.7
5
76.8
477
.16
77.4
878
.40
127.
5312
9.03
129.
3013
3.31
168.
71
63
6
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
4.07
1.00
3.02
4.16
4.09
2.00
2.01
-0.0
03.
283.
293.
293.
303.
313.
323.
333.
363.
383.
403.
425.
655.
665.
675.
675.
685.
695.
695.
705.
717.
047.
067.
077.
087.
087.
087.
097.
107.
107.
107.
117.
127.
127.
167.
277.
277.
297.
307.
317.
327.
347.
347.
417.
427.
427.
427.
437.
437.
437.
457.
457.
457.
467.
477.
477.
487.
487.
497.
497.
827.
827.
827.
847.
848.
188.
188.
188.
198.
208.
208.
21
O
O
Ph Br Br
O
Ph
SePh
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
32.4
2
50.1
0
61.4
3
72.2
476
.84
77.1
677
.48
127.
2912
8.03
128.
3312
9.24
129.
5212
9.88
129.
9113
1.27
132.
0313
2.97
133.
1213
3.53
165.
61
188.
12
64
7
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
f1 (ppm)
2.07
2.00
0.47
0.51
4.82
3.05
1.97
3.04
2.02
3.01
3.03
3.05
3.07
3.10
3.12
3.12
3.14
3.15
3.16
3.22
3.36
3.39
3.39
3.41
3.42
3.44
3.45
3.46
3.47
3.48
3.50
3.50
3.52
3.53
7.03
7.05
7.06
7.07
7.08
7.08
7.08
7.09
7.10
7.10
7.11
7.12
7.17
7.18
7.19
7.19
7.21
7.21
7.22
7.23
7.24
7.24
7.26
7.26
7.26
7.30
7.43
7.44
7.46
7.46
7.52
7.53
7.54
7.54
7.55
7.55
7.56
7.57
7.75
7.75
7.76
7.77
7.81
7.82
7.82
7.83
7.84
O
Se
Ph
O
Ph
Ph
O
-100102030405060708090100110120130140150160170180190200210
f1 (ppm)
38.9
339
.03
57.5
558
.95
75.8
776
.03
76.8
477
.16
77.4
811
1.36
111.
6412
5.78
126.
2412
7.70
127.
7612
7.80
128.
9112
9.20
129.
3212
9.36
129.
4412
9.85
129.
9113
0.33
130.
3713
1.55
131.
6213
1.66
138.
4413
9.43
140.
36
164.
2016
4.46
193.
1219
3.15