activated allenes with ambient air as sole oxidant visible-light … · 2016. 11. 11. · 1...
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Supporting Information
Visible-light induced phenylchalcogenyl-oxygenation of activated allenes with ambient air as sole oxidantGullapalli Kumaraswamy,* Swargam Vijaykumar, Kukkadapu Ankamma and Vykunthapu Narayanarao
Table of Contents
1. General information, Synthetic procedure & References 2-6
2. Copies of 1H and 13C NMR spectra for all compounds 7-49
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2016
2
General information:
All reactions were conducted under open air atmosphere. Apparatus used for reactions were oven dried. THF was
distilled over sodium benzophenone ketyl before use. MeCN purchased directly from the commercial suppliers and
used without further purification. Starting materials (1a, 8a, 4m-q),1 8c,2 4j, 4k, 4l, 6a, 10a,3 4b,4 4c5 4d,6 4e,7 4f-g,8 and
4q9 were prepared according to the reported procedure. All other chemicals used were commercially available. Progress
of the reactions was monitored by TLC on pre-coated silica gel 60 F-254. Evaporation of solvents was performed at
reduced pressure on a rotary evaporator. Column chromatography was carried out with silica gel grade 60-120 and 100-
200 mesh. 1H NMR spectra were recorded at 300, 400 & 500 MHz and 13C NMR 75, 100 &125 MHz in CDCl3. Chemical
shifts () are reported in ppm. Tetramethylsilane (δ = 0.00 ppm for 1H) and CDCl3 (δ = 77.00 ppm for 13C) were used as
the internal standard. Scalar coupling constants (J) are reported in hertz (Hz). The following abbreviations are used to
designate the multiplicities: s = singlet, d = doublet, t = triplet, dd = doublet of doublet, ddd = doublet of doublet of
doublet, m = multiplet, br.s = broad singlet. Mass spectral data were compiled using MS (ESI), and High resolution
mass spectra (HRMS) were recorded by ESI probe in positive mode using ORBITRAP analyzer.
Electrochemical measurements were performed on a PC-controlled CH instruments model CHI 620C electrochemical
analyzer. The experiments were performed in a 1 mM phenyl allene solution in CAN at scan rate of 100 mV s-1using 0.1
M tetrabutyl ammonium perchlorate (TBAP) as supportingelectrolyte. The working electrode was glassy carbon, a
standard calomel electrode (SCE) was the reference electrode and platinum wire was an auxiliary electrode. After a
cyclic voltammogram (CV) had been recorded, ferrocene was added, and a second voltammogram was measured.
The UV spectrum was recorded on a HITACHI U-2910 double beam UV/VIS spectrophotometer.
3
Figure 1. 3-Phenyl propa-1,2-diene 1a oxidation potential in MeCN
0.0 -0.2 -0.4 -0.6 -0.8 -1.0 -1.2 -1.4 -1.6 -1.8
B
A
Phenyl allene (red)in ACN
-1.22 V
Figure 2. 3-Phenyl propa-1,2-diene 1a reductive potential in MeCN
4
250 300 350 400 450 5000.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Wavelength (nm)
Diphenyl diselenideAb
sorb
ance
Phenyl allene
Absorption spectra in
300 400 5000.0
0.5
1.0
1.5
2.0
2.5
3.0
Abso
rban
ce
Wavelength (nm)
Diphenyl diselenide
240 280 3200.0
0.2
0.4
0.6
0.8
1.0
Abso
rban
ce
Wavelength (nm)
Phenyl alleneλmax = 331nm
λmax = 230nm
Absorption spectra in
Figure 3. UV spectrum of 3-phenyl propa-1,2-diene 1a and PhSeSePh, 2a in MeCN
.
5
Figure 4. Irradiation of reaction mixture with two 7W Day light white LED bulbs [6500K, 42mA (220-240Vac 50Hz) PHILIPS, Made in India]
References:[1] a) Baird, M. S.; Nizovtsev, A. V.; Bolesov, G. I. Tetrahedron, 2002 , 58, 1581-1593; b) Hu, J.; Xie, Y.; Huang, H.
Angew. Chem., Int. Ed. 2014, 126, 7400-7404.
[2] Zhu, C.; Yang, B.; Qiu, Y.; Bäckvall, J.-E. Chemistry - A European Journal, 2016, 22, 2939-2943.
[3] Fernanda, M.; Ribeiro, L.; Ribeira, S. B.; Clara, Gomes, M. V. D.; Teres, P. M. Tetrahedron 2013, 69, 10081-10090.
[4] Fan, G.; Xie, X.; Liu, Y.; Li, Y. Organometallics 2013, 32, 1636-1642.
[5] Nakamura, H.; Onagi, S.; Kamakura, T. J. Org. Chem. 2005, 70, 2357-2360.
[6] Liu, J.; Ma, S. Tetrahedron 2013, 69, 10161-10167.
[7] Rout, L.; Aarned, A. M. Chemistry - A European Journal, 2009, 15, 12926.
[8] Guo, H.; Qian, R.; Guo, Y.; Ma, S. J. Org. Chem. 2008, 73, 7934-7938.
[9] Periaswamy, M.; Sanjeeva Kumar, N.; Dalai, M.; Gurubramam, R.; Obul Reddy, P. Organic Letters, 2012, 14, 2932-
2935.
6
TLC images of 3a with different intervals:
7
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5f1 (ppm)
9.00
1.44
0.00
9.48
9.78
3aZ:E mixture spectra (crude)
8
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
3.00
2.43
3.08
2.02
1.08
1.00
1.60
7.18
7.19
7.19
7.19
7.20
7.20
7.20
7.21
7.26
7.32
7.37
7.37
7.38
7.39
7.39
7.39
7.39
7.40
7.40
7.40
7.40
7.42
7.43
7.43
7.44
7.44
7.84
7.85
7.85
7.86
7.86
8.01
9.50
0102030405060708090100110120130140150160170180190200
76.7
577
.00
77.2
5
127.
2712
8.47
129.
2113
0.86
131.
0513
1.93
132.
3113
4.20
152.
35
191.
37
H
SePh
HO
3a
H
SePh
HO
3a
9
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
2.27
1.17
6.34
2.34
1.00
0.00
7.22
7.23
7.23
7.24
7.26
7.32
7.36
7.37
7.38
7.40
7.41
7.65
7.66
7.67
7.67
9.79
0102030405060708090100110120130140150160170180190f1 (ppm)
76.6
877
.00
77.3
2
126.
6112
8.58
129.
0112
9.33
129.
5412
9.82
136.
43
145.
47
188.
97
E-3a
E-3a
10
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
11.3
09.
3728
.38
23.2
5
5.43
5.41
1.00
7.07
7.09
7.10
7.17
7.19
7.26
7.35
7.36
7.59
7.61
8.14
9.29
9.63
105110115120125130135140145150155160165170175180185190195200f1 (ppm)
112.
75
124.
24
127.
9412
8.14
129.
1013
0.24
135.
31
138.
20
140.
8914
1.35
156.
88
193.
45
H
TePh
HO
3abZ:E=9:1mix
H
TePh
HO
3abZ:E=9:1mix
11
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
3.09
2.85
2.28
1.88
1.96
1.03
1.00
1.58
2.39
7.17
7.18
7.19
7.19
7.19
7.20
7.20
7.23
7.25
7.25
7.37
7.37
7.38
7.38
7.39
7.39
7.39
7.40
7.79
7.81
7.98
9.48
-100102030405060708090100110120130140150160170180190200210
21.5
9
76.6
877
.00
77.3
2
127.
0612
9.15
129.
2412
9.48
130.
8813
1.31
131.
3913
1.58
141.
71
153.
30
191.
45
H
SePh
HO
3b
H
SePh
HO
3b
12
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
9.11
2.83
1.93
1.97
1.91
0.99
1.00
1.33
7.38
7.38
7.39
7.39
7.39
7.39
7.40
7.44
7.44
7.45
7.46
7.46
7.46
7.83
7.85
7.99
9.48
-100102030405060708090100110120130140150160170180190200210
31.1
4
35.1
1
76.7
877
.10
77.4
1
125.
6012
7.17
129.
2612
9.59
131.
1113
1.30
131.
5013
1.74
153.
0815
4.88
191.
55
H
SePh
HO
3c
H
SePh
HO
3c
13
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
9.44
2.23
1.28
10.6
76.
122.
072.
801.
19
1.00
1.31
7.17
7.19
7.26
7.34
7.36
7.38
7.39
7.44
7.45
7.46
7.46
7.63
7.64
7.65
7.67
7.82
7.84
7.85
9.82
0102030405060708090100110120130140150160170180190f1 (ppm)
31.0
8
35.0
8
76.6
877
.00
77.3
2
125.
2912
5.54
125.
8712
5.96
128.
8212
9.54
129.
6412
9.73
130.
2713
1.22
131.
9613
6.15
136.
5614
3.94
146.
07
152.
99
156.
44
188.
9719
1.49
E-3c
E-3c
14
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.53.
203.
062.
92
0.94
2.75
1.83
1.00
1.00
1.00
1.55
2.22
2.24
2.33
6.98
7.15
7.16
7.17
7.17
7.18
7.26
7.34
7.34
7.34
7.35
7.35
7.36
7.36
7.38
8.12
9.52
-100102030405060708090100110120130140150160170180190200210
-0.0
1
19.3
019
.39
19.7
0
76.7
577
.00
77.2
5
127.
1612
9.00
129.
3712
9.71
130.
7013
0.92
131.
6413
2.27
133.
6213
5.12
136.
3413
9.44
145.
91
151.
07
191.
29
H
SePh
HO
3d
H
SePh
HO
3d
15
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
3.02
2.03
3.02
2.17
3.23
1.00
1.58
3.86
6.93
6.93
6.94
6.95
6.95
6.96
7.17
7.18
7.18
7.19
7.19
7.20
7.21
7.26
7.36
7.36
7.37
7.37
7.38
7.38
7.39
7.94
7.95
7.96
7.97
7.97
7.98
9.48
-100102030405060708090100110120130140150160170180190200
55.4
2
76.6
877
.00
77.3
2
114.
02
126.
8212
6.94
128.
8612
9.19
129.
7413
1.24
133.
63
153.
65
162.
06
191.
59
H
SePh
HO
3eMeO
H
SePh
HO
3eMeO
16
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
6.12
0.95
1.96
2.88
1.91
1.05
1.00
3.79
6.53
6.53
6.54
6.54
6.55
6.55
7.03
7.03
7.04
7.04
7.20
7.20
7.21
7.92
7.92
9.48
-100102030405060708090100110120130140150160170180190200210
55.4
0
103.
38
108.
83
127.
2312
9.18
131.
4113
1.79
132.
4313
5.77
152.
22
160.
48
191.
31
H
SePh
HO
3f OMe
MeO
H
SePh
HO
3f OMe
MeO
17
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
1.91
2.87
1.84
1.87
0.94
1.00
7.07
7.08
7.08
7.10
7.10
7.12
7.12
7.18
7.18
7.19
7.20
7.20
7.21
7.26
7.35
7.36
7.36
7.36
7.37
7.37
7.38
7.38
7.38
7.39
7.87
7.87
7.88
7.89
7.90
7.90
7.91
7.95
9.49
-100102030405060708090100110120130140150160170180190200210
115.
6011
5.81
127.
3412
8.98
129.
2813
0.37
130.
4013
1.80
133.
2713
3.35
151.
06
162.
7116
5.23
191.
30
H
SePh
HO
3gF
H
SePh
HO
3gF
18
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
0.92
2.80
1.86
1.84
1.06
1.00
6.82
6.82
6.83
6.84
6.84
6.85
6.85
6.86
6.86
7.22
7.22
7.26
7.38
7.40
7.83
9.47
-100102030405060708090100110120130140150160170180190200210
105.
4010
5.60
105.
8011
3.20
113.
3611
3.41
127.
8112
8.12
129.
3913
0.04
135.
4213
6.83
136.
9613
7.04
147.
28
161.
5416
1.64
163.
5216
3.62
190.
77H
SePh
HO
3h
F
F
H
SePh
HO
3h
F
F
19
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
2.91
1.87
0.94
1.05
1.91
1.00
7.13
7.14
7.16
7.18
7.19
7.26
7.33
7.33
7.35
7.35
7.82
7.95
8.11
9.55
-100102030405060708090100110120130140150160170180190200210
121.
8212
3.23
124.
0012
7.48
128.
0412
9.46
129.
8813
1.60
131.
8713
2.87
136.
1513
7.60
145.
68
190.
67
H
SePh
HO
3i
F3C
CF3
H
SePh
HO
3i
F3C
CF3
20
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
3.04
1.03
2.88
1.93
1.96
1.06
1.00
2.29
2.29
7.01
7.02
7.04
7.06
7.18
7.18
7.19
7.19
7.19
7.19
7.20
7.20
7.21
7.26
7.35
7.35
7.36
7.36
7.37
7.37
7.37
7.37
7.38
7.38
7.38
7.69
7.70
7.71
7.73
7.92
9.48
-100102030405060708090100110120130140150160170180190200210
14.5
214
.54
76.6
877
.00
77.3
2
115.
1511
5.38
125.
1412
5.32
127.
2412
9.12
129.
2113
0.04
130.
0713
0.70
130.
7813
1.52
131.
75
151.
57
161.
3516
3.87
191.
35
H
SePh
HO
3jF
H
SePh
HO
3jF
21
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5f1 (ppm)
3.17
1.07
1.60
0.39
1.03
3.69
0.94
0.93
0.13
0.10
1.00
1.56
2.27
6.97
6.99
7.01
7.05
7.07
7.24
7.26
7.38
7.39
7.40
7.40
7.64
7.64
7.65
7.66
9.48
9.76
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
14.4
6
76.6
877
.00
77.3
2
115.
22
125.
6812
6.62
129.
0112
9.69
129.
8213
2.73
136.
3413
6.56
144.
61
160.
6416
3.17
188.
6919
1.40
E-3j
E-3j
22
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
2.87
1.94
1.99
1.06
1.97
1.00
1.56
7.19
7.20
7.21
7.22
7.23
7.23
7.26
7.37
7.38
7.39
7.39
7.86
7.88
7.98
8.22
8.23
9.51
-100102030405060708090100110120130140150160170180190200210
76.7
577
.00
77.2
5
123.
4712
7.81
128.
0212
9.47
131.
0713
2.76
136.
94
146.
0414
8.05
190.
66
H
SePh
HO
3kO2N
H
SePh
HO
3kO2N
23
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5
2.74
2.85
1.97
4.02
1.88
1.00
1.00
1.57
7.18
7.19
7.19
7.20
7.20
7.21
7.21
7.24
7.36
7.37
7.37
7.38
7.38
7.39
7.39
7.40
7.40
7.40
7.41
7.41
7.41
7.42
7.44
7.44
7.45
7.46
7.47
7.47
7.61
7.61
7.62
7.62
7.63
7.64
7.64
7.65
7.66
7.66
7.95
7.96
8.02
9.51
-100102030405060708090100110120130140150160170180190200210
76.6
877
.00
77.3
2
127.
0212
7.05
127.
2412
8.05
128.
9012
9.22
129.
2813
1.71
131.
8313
1.92
133.
0513
9.82
143.
56
152.
02
191.
32
H
SePh
HO
3lPh
H
SePh
HO
3lPh
24
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5
1.87
2.81
3.25
4.03
2.90
1.00
1.57
6.95
6.97
6.98
6.98
6.99
7.00
7.01
7.01
7.04
7.05
7.05
7.06
7.06
7.06
7.07
7.07
7.08
7.08
7.10
7.10
7.17
7.18
7.19
7.19
7.19
7.19
7.20
7.21
7.21
7.23
7.26
7.32
7.36
7.36
7.36
7.37
7.37
7.37
7.38
7.38
7.39
7.39
7.39
7.40
7.41
7.41
7.43
7.49
7.84
7.86
7.89
7.90
7.91
7.92
7.92
7.93
7.95
7.96
7.97
9.48
9.49
9.80
-100102030405060708090100110120130140150160170180190200210
76.7
577
.00
77.2
511
7.61
117.
8311
8.07
119.
6912
0.06
120.
1812
4.50
124.
6812
6.83
127.
1212
8.64
129.
2512
9.48
129.
7713
0.00
130.
0713
0.25
131.
3513
1.52
133.
2613
3.41
144.
74
152.
5215
5.38
155.
4415
5.57
160.
2816
0.62
186.
51
191.
52
H
SePh
HO
3mPhO
Z:E=8:2
H
SePh
HO
3mPhO
Z:E=8:2
25
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
3.26
1.07
3.84
1.97
2.24
0.98
1.02
1.01
1.00
3.94
7.12
7.13
7.17
7.17
7.17
7.18
7.19
7.19
7.26
7.40
7.41
7.42
7.42
7.43
7.74
7.77
8.06
8.06
8.08
8.09
8.12
8.27
9.54
0102030405060708090100110120130140150160170180190200
55.8
3
76.6
877
.00
77.3
2
105.
71
119.
6012
6.82
127.
0812
7.85
128.
1412
9.18
129.
4612
9.62
130.
5813
0.71
131.
5713
2.68
135.
91
153.
51
159.
43
191.
55
SePh
H O
3nMeO
SePh
H O
3nMeO
26
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1 (ppm)
2.98
1.15
1.32
2.04
2.20
0.45
1.06
0.42
1.00
1.56
3.97
7.19
7.19
7.22
7.23
7.23
7.24
7.25
7.26
7.79
7.81
7.82
7.85
7.86
7.89
7.91
7.92
7.92
7.93
7.94
8.01
8.03
8.26
8.49
10.1
0
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
55.4
8
76.6
877
.00
77.3
2
105.
9110
6.12
119.
9612
3.66
125.
9212
7.62
131.
1113
1.61
132.
3613
3.55
134.
2313
8.28
160.
26
192.
00
E-3n
E-3n
27
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
5.83
3.83
1.06
1.93
2.05
0.90
2.00
1.58
7.17
7.18
7.18
7.19
7.20
7.21
7.26
7.36
7.37
7.38
7.38
7.45
7.46
7.48
7.81
7.82
7.83
7.98
8.30
9.51
-100102030405060708090100110120130140150160170180190200
127.
4812
8.60
128.
8112
9.30
132.
1013
2.60
132.
7913
3.60
134.
49
150.
19
191.
14
H
SePh
OH
H
SePh
HO
5a
H
SePh
OH
H
SePh
HO
5a
28
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
1.62
1.97
2.01
3.91
1.00
1.83
1.00
1.82
4.16
7.11
7.13
7.13
7.15
7.26
7.30
7.31
7.33
7.33
7.34
7.35
7.35
7.36
7.37
7.37
7.38
7.39
7.39
7.40
7.41
7.41
7.65
7.65
7.67
7.67
7.69
7.69
7.74
7.74
7.74
7.75
7.76
7.76
7.76
8.70
8.72
-100102030405060708090100110120130140150160170180190200210
67.0
1
76.6
877
.00
77.3
2
120.
9212
2.84
124.
2312
8.18
128.
8512
9.13
136.
4013
6.99
141.
87
147.
71
155.
29
H
NSePh
OH
5bc
H
NSePh
OH
5bc
29
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
2.77
1.95
1.03
1.82
1.08
1.00
1.58
7.20
7.21
7.21
7.22
7.22
7.23
7.23
7.24
7.24
7.26
7.38
7.38
7.38
7.39
7.40
7.87
9.06
9.16
9.54
-100102030405060708090100110120130140150160170180190200
76.7
577
.00
77.2
5
127.
5912
8.19
128.
7112
9.61
130.
2513
2.80
137.
6414
1.94
157.
3515
8.71
190.
21
H
NN
SePh
HO
5c
H
NN
SePh
HO
5c
30
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
2.94
2.09
1.29
2.13
2.23
1.15
1.00
1.56
7.26
7.38
7.38
7.39
7.40
7.41
7.41
7.42
7.43
7.51
7.52
7.54
7.60
7.62
7.66
7.66
7.68
7.68
8.06
8.06
8.08
8.13
9.31
-100102030405060708090100110120130140150160170180190200210
76.6
877
.00
77.3
2
123.
2012
6.59
128.
4612
8.90
129.
5212
9.72
131.
5113
3.44
135.
8113
7.29
152.
79
189.
83
H
OSePh
HO
5d
H
OSePh
HO
5d
31
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
2.26
0.99
8.81
2.10
1.00
1.57
5.27
6.95
7.26
7.34
7.35
7.35
7.36
7.36
7.37
7.39
7.39
7.39
7.40
7.41
7.42
7.62
7.62
7.64
9.18
-100102030405060708090100110120130140150160170180190200
67.1
2
76.7
577
.00
77.2
5
122.
0412
5.40
128.
4312
8.48
128.
6312
9.45
129.
7213
0.30
135.
2913
5.91
150.
87
166.
00
188.
97
H
SePh
OH
OO
5e
H
SePh
OH
OO
5e
32
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.5
1.01
17.0
4
1.00
6.47
6.52
7.26
7.38
7.40
7.42
7.43
7.44
7.45
7.46
7.48
7.50
7.51
7.52
7.52
7.54
7.56
7.56
7.58
10.8
9
-100102030405060708090100110120130140150160170180190200
76.7
577
.00
77.2
5
119.
4012
5.55
128.
7812
8.88
129.
8813
0.20
130.
6513
0.72
130.
8013
1.35
132.
2013
2.21
133.
0213
7.23
158.
38
189.
5218
9.59
(Ph)2PO
SePh
HOH
5f
(Ph)2PO
SePh
HOH
5f
33
-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
2.00
2.17
2.66
1.94
4.33
8.47
1.00
1.68
6.77
6.77
6.79
6.79
7.16
7.18
7.24
7.25
7.25
7.26
7.27
7.31
7.38
7.39
7.40
7.40
7.49
7.49
7.51
7.51
7.53
7.53
7.54
7.55
7.55
7.57
10.0
9
-100102030405060708090100110120130140150160170180190200
76.7
577
.00
77.2
5
125.
7112
8.28
128.
3812
8.56
128.
9912
9.01
129.
0412
9.37
130.
2713
1.11
131.
9313
2.01
132.
1713
2.18
132.
2713
2.35
136.
2713
8.84
152.
7915
2.86
190.
7819
0.83
(Ph)2PO
SePh
HO
5g
Ph
(Ph)2PO
SePh
HO
5g
Ph
34
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
2.06
3.76
1.10
4.26
1.37
2.20
1.00
1.23
5.18
5.20
7.26
7.27
7.28
7.28
7.32
7.33
7.34
7.45
7.46
7.48
7.50
7.50
7.50
7.51
7.58
7.58
7.59
7.60
7.60
7.62
8.05
8.07
9.42
-100102030405060708090100110120130140150160170180190200
63.9
5
76.7
577
.00
77.2
5
127.
8712
8.22
128.
5012
9.16
129.
3212
9.47
129.
7313
1.49
132.
8813
3.44
136.
54
152.
16
166.
09
189.
79
H
SePh
OH
O
O5h
H
SePh
OH
O
O5h
35
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
3.37
3.22
1.98
2.16
1.03
1.00
1.57
7.25
7.26
7.26
7.27
7.36
7.37
7.38
7.40
7.40
7.40
7.41
7.49
7.50
7.50
7.51
7.51
7.61
7.61
7.62
7.62
8.83
9.27
-100102030405060708090100110120130140150160170180190200
76.6
877
.00
77.3
2
127.
5412
9.09
129.
3112
9.80
131.
9613
2.32
133.
0813
3.34
133.
63
165.
93
186.
32
PhSe
H
SePh
HO
5i
PhSe
H
SePh
HO
5i
36
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.5
1.04
5.75
2.18
1.04
1.06
1.16
1.00
1.56
7.24
7.25
7.25
7.26
7.27
7.28
7.36
7.37
7.37
7.38
7.39
7.39
7.69
7.69
7.71
7.71
7.77
7.78
9.84
11.0
5
-100102030405060708090100110120130140150160170180190200210
76.6
877
.00
77.3
2
119.
0811
9.78
121.
4312
7.19
127.
7112
9.17
129.
4213
1.65
131.
8613
5.30
139.
7914
3.29
161.
55
196.
06
O
H
SePh
OH
CHO
5j
O
H
SePh
OH
CHO
5j
37
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
2.07
0.96
1.21
3.34
1.29
3.22
0.76
1.01
0.93
1.57
4.94
4.95
6.77
6.79
7.08
7.26
7.29
7.30
7.30
7.31
7.39
7.40
7.41
7.49
7.50
7.50
7.50
7.50
7.51
7.85
7.85
7.87
7.87
9.46
-100102030405060708090100110120130140150160170180190200210
67.4
7
76.7
577
.00
77.2
5
112.
31
121.
5812
5.07
128.
1112
9.06
129.
6013
3.02
135.
3513
5.88
136.
86
151.
98
159.
60
189.
2318
9.43
SePhO
5l
OH
H
CHO
SePhO
5l
OH
H
CHO
38
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
3.00
6.05
4.35
0.82
2.60
2.62
7.17
7.19
7.21
7.22
7.24
7.26
7.27
7.30
7.33
7.35
7.37
7.40
7.42
7.44
7.49
7.51
9.32
9.90
0102030405060708090100110120130140150160170180190200
28.3
8
125.
4112
6.86
128.
2312
8.53
128.
6012
9.21
129.
3713
0.78
131.
3913
1.54
131.
7613
3.52
133.
6513
4.78
139.
73
167.
66
189.
55
SePhO
7c
OH
H
CHO
SePh
OH
5mZ : E = 10:1
SePh
OH
5mZ : E = 10:1
39
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
3.48
4.68
5.31
22.0
14.
332.
451.
20
0.96
1.00
7.09
7.11
7.12
7.12
7.13
7.14
7.15
7.19
7.19
7.20
7.20
7.21
7.21
7.24
7.25
7.26
7.27
7.27
7.28
7.28
7.30
7.30
7.31
7.31
7.33
7.36
7.36
7.37
7.38
7.38
7.39
7.40
7.42
7.43
7.43
7.44
7.44
7.45
7.46
7.46
7.47
9.43
-100102030405060708090100110120130140150160170180190200
126.
9112
8.00
128.
4112
8.95
129.
3012
9.63
130.
1213
0.93
131.
1913
2.31
134.
8213
9.48
141.
94
166.
22
189.
97
SePh
OH
5n
SePh
OH
5n
40
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
3.33
2.62
2.36
2.12
29.4
0
1.00
0.90
3.81
3.84
6.78
6.79
6.88
6.89
6.90
7.11
7.12
7.14
7.16
7.20
7.20
7.22
7.25
7.26
7.27
7.28
7.29
7.31
7.32
7.32
7.33
7.37
7.38
7.40
7.43
7.45
7.46
9.36
9.43
-100102030405060708090100110120130140150160170180190200
55.3
655
.48
113.
2911
3.84
127.
9412
8.36
128.
9112
9.86
131.
4013
1.86
132.
0713
3.20
139.
8714
2.18
160.
7716
1.55
166.
2816
6.64
189.
8919
0.04
SePh
OH
MeO 5oZ : E = ~1:1
SePh
OH
MeO 5oZ : E = ~1:1
41
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
10.9
54.
023.
131.
35
1.00
7.10
7.12
7.13
7.14
7.15
7.16
7.16
7.18
7.19
7.20
7.21
7.22
7.26
7.36
7.38
7.40
7.44
7.45
7.47
9.41
-100102030405060708090100110120130140150160170180190
127.
1012
8.14
128.
7512
8.89
128.
9912
9.48
129.
6213
0.59
132.
3713
2.57
135.
6113
6.44
137.
9114
1.56
164.
01
189.
49
SePh
OH
Cl 5p
SePh
OH
Cl 5p
42
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
7.16
8.86
1.01
0.82
1.00
7.09
7.10
7.10
7.11
7.12
7.12
7.13
7.13
7.13
7.14
7.15
7.15
7.16
7.16
7.17
7.18
7.18
7.18
7.19
7.25
7.25
7.25
7.26
7.26
7.26
7.27
7.27
7.28
7.28
7.29
7.30
7.30
7.30
7.31
7.32
7.34
7.35
7.35
7.36
7.37
7.38
9.42
-100102030405060708090100110120130140150160170180190200
127.
1512
7.49
129.
0113
0.34
130.
6313
1.06
131.
1913
2.60
135.
2913
5.75
135.
8213
5.89
139.
1514
0.24
164.
18
189.
80
SePh
OH
Cl
(E)-5p
SePh
OH
Cl
(E)-5p
43
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
1.17
0.86
1.32
1.39
1.55
0.59
1.01
1.00
3.66
6.92
6.94
6.96
6.97
7.03
7.05
7.06
7.08
7.09
7.11
7.14
7.14
7.15
7.15
7.16
7.16
7.17
7.32
7.33
7.33
7.34
7.34
7.35
7.36
7.38
7.39
7.39
7.42
7.43
7.44
7.45
7.48
7.48
7.49
7.51
7.55
7.57
7.64
7.65
7.72
7.74
7.82
7.84
0102030405060708090100110120130140150160170180190
127.
6712
7.75
127.
7912
7.98
128.
1312
8.27
128.
3312
8.45
128.
5312
9.04
129.
1112
9.30
129.
5412
9.79
130.
4213
1.77
132.
6113
3.48
134.
1013
4.38
134.
7113
5.31
135.
4813
6.96
137.
2613
8.89
194.
6619
5.07
HPh
O
SePh
5qZ : E = 20:1
HPh
O
SePh
5qZ : E = 20:1
44
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5
0.87
0.95
0.07
0.07
0.40
1.56
1.00
1.55
4.15
4.22
4.24
4.39
4.41
4.43
4.65
4.66
4.80
4.81
5.53
6.11
6.57
6.58
6.59
6.91
6.93
7.24
7.25
7.27
7.28
7.29
7.30
7.30
7.31
7.31
7.32
7.50
7.50
7.51
7.52
7.53
7.54
7.55
7.55
7.57
7.57
-100102030405060708090100110120130140150160170180190200210
42.5
9
48.5
3
62.1
964
.49
67.1
170
.93
76.6
877
.00
77.3
2
114.
7411
4.89
121.
0712
1.45
123.
6912
7.88
128.
0012
8.10
129.
5012
9.53
131.
5513
3.23
134.
0013
4.13
134.
57
158.
18
SePhO
OH
7a
SePhO
OH
7a
45
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0
0.79
3.29
3.32
2.00
1.98
0.90
1.79
2.80
2.23
3.30
2.22
1.25
1.57
2.43
2.44
4.01
4.29
4.30
5.87
5.88
5.90
7.18
7.20
7.20
7.21
7.22
7.23
7.25
7.26
7.27
7.28
7.28
7.28
7.29
7.30
7.30
7.31
7.31
7.32
7.32
7.48
7.49
-100102030405060708090100110120130140150
21.5
7
42.4
7
48.8
3
76.7
577
.00
77.2
5
127.
6912
8.05
128.
1712
8.57
128.
8312
9.14
129.
3812
9.55
132.
9813
3.40
134.
0013
5.19
138.
8414
3.71
H
N SePhPh
Tos
OH
7b
H
N SePhPh
Tos
OH
7b
46
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5
0.85
2.20
2.21
1.00
6.40
5.34
2.00
0.91
1.26
1.55
4.28
4.88
4.90
6.04
6.06
6.07
7.12
7.13
7.14
7.15
7.17
7.17
7.20
7.21
7.21
7.23
7.26
7.28
7.30
7.31
7.32
7.32
7.33
7.34
7.35
7.36
7.37
7.54
7.54
7.56
7.56
7.76
7.76
-100102030405060708090100110120130140150160
42.2
1
45.0
3
76.7
577
.00
77.2
5
96.9
6
111.
20
114.
4712
3.31
125.
7612
5.86
127.
6912
8.72
129.
0712
9.63
131.
5113
2.01
132.
7413
3.36
133.
6313
4.79
135.
1313
5.37
H
NPhSe
SePh
Br
OH
7c
H
NPhSe
SePh
Br
OH
7c
47
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
0.70
2.00
2.04
0.67
0.94
0.30
2.47
12.0
1
5.16
3.16
3.18
3.56
3.58
3.73
3.86
5.91
5.92
5.94
6.06
6.08
6.10
6.99
7.01
7.04
7.17
7.17
7.19
7.19
7.21
7.21
7.22
7.23
7.24
7.25
7.25
7.26
7.27
7.40
7.41
7.42
7.42
7.43
7.46
7.47
7.47
7.48
7.49
7.50
7.55,
-100102030405060708090100110120130140150160170180190200210
31.3
034
.92
37.2
639
.04
126.
1312
7.21
127.
4612
7.78
128.
4612
8.93
129.
2512
9.55
129.
8313
0.29
131.
5613
2.81
133.
3913
4.26
134.
7413
6.29
137.
5113
9.28
139.
64
SePh
SePh9a
Z : E = 3:1
SePh
SePh9a
Z : E = 3:1
48
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0
2.13
2.13
1.18
1.56
2.32
1.93
2.09
3.34
3.16
2.82
0.98
0.98
2.02
2.04
0.96
0.95
6.00
6.13
3.64
3.64
0.90
0.91
0.93
0.93
0.95
0.97
0.98
1.06
1.08
1.10
1.12
1.19
1.21
1.23
1.26
1.27
1.48
1.50
1.57
1.61
1.63
2.43
2.47
2.49
2.51
3.62
5.54
5.56
7.21
7.25
7.26
7.44
7.45
7.46
-100102030405060708090100110120130140150160170180190
25.5
925
.88
32.5
232
.70
37.9
341
.04
126.
5612
6.98
127.
4312
7.75
128.
8412
9.21
131.
5413
2.68
134.
54
144.
12
SePhSePh
9b
SePhSePh
9b
49
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.52.
00
1.32
1.34
1.89
2.04
1.33
0.70
2.25
1.55
4.79
14.9
36.
71
2.67
2.68
3.10
3.11
3.33
3.82
3.87
3.92
4.97
4.98
4.98
5.00
5.02
5.04
5.62
5.63
5.64
5.65
5.66
5.67
5.68
5.70
7.09
7.11
7.12
7.14
7.17
7.19
7.20
7.23
7.23
7.25
7.26
7.27
7.28
7.29
7.30
7.41
7.43
7.45
7.46
7.46
7.48
7.49
-100102030405060708090100110120130140150160170180190200
33.3
733
.75
35.7
337
.16
40.9
642
.34
116.
2812
6.20
126.
3312
7.10
127.
4512
8.47
128.
8812
9.16
132.
6413
2.86
134.
3513
4.52
134.
8013
5.10
138.
6013
9.12
143.
8514
4.29
SePh
SePh
9c
Z : E = 3:2
SePh
SePh
9c
Z : E = 3:2
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