Supporting Information
Table of Contents
I. General remarks ……………………………...... ………...... 2
II. Synthesis procedure for compounds 3 …….………………...……………..….………………….2
III. Analytical data of products obtained in this study………….…………...……..……..………2-9
IV. 1H NMR and 13C NMR spectra copies of compounds 3..…………………….10-30
2
I. General Remarks:
Unless otherwise stated, all commercial reagents and solvents were used without additional purification. All the reactions were carried out under air atmosphere. 1H NMR spectra of compounds 3 were recorded at 25ºC on a Bruker AscendTM 400 spectrometer. Chemical shifts (in ppm) were referenced TMS in CDCl3 (0 ppm). 13C-NMR spectra were obtained by using the same NMR spectrometers and were calibrated with CDCl3 (δ = 77.00 ppm). Melting points were obtained with a micro melting point XT4A Beijing Keyi electrooptic apparatus and are uncorrected. HRMS data were obtained on a Waters LCT PremierxeTM (USA). All reactions were monitored by TLC with Taizhou GF254 silica gel coated plates. Flash column chromatography was carried out using 200-300 mesh silica gel at increased pressure.
II. Synthesis procedure for compounds 3 (1a as an example).
Styrene 1a (0.3 mmol), 4-methyl benzene sulfonyl hydrazine 2a (0.6 mmol), diphenyl diselenide (0.3 mmol), K2S2O8 (0.6 mmol), KI (0.2 equiv), and CH3CN (2.0 mL) at 20 oC for 12 h (monitored by TLC), quenched with water, extracted with dichloromethane (5×3 ml), and dried over anhydrous Na2SO4. The solvent was removed under reduced pressure, and the residue was purified by a shot flash silica gel column chromatography (EtOAc/petro ether = 1:8) to give compound 3a as a white solid (111.1 mg, 89%).
III. Analytical data of products obtained in this study
phenyl(2-phenyl-2-tosylethyl)selane 3a
White solid. Mp: 120-122 oC; 1H NMR (400 MHz; CDCl3): δ = 2.34 (s, 3H), 3.64 (dd, J1 = 3.2 Hz, J2 = 14.8 Hz, 1H), 4.01 (q, J = 11.6 Hz, 1H), 4.70 (dd, J1 = 3.2 Hz, J2 = 11.2 Hz, 1H), 7.03-7.11 (m, 7H), 7.26 (t, J = 7.2 Hz, 2H), 7.31-7.43 (m, 5H). 13C NMR (100 MHz; CDCl3): δ = 21.5, 39.9, 61.2, 127.5, 127.7, 127.9, 128.4, 128.5, 128.7, 129.3, 129.5, 135.4, 136.2, 137.7, 144.3. HRMS (ESI-TOF) Calcd for C21H21O2SSe, [M+H]+ 417.0425; Found 417.0429. IR (KBr, cm-1): 3026, 2915, 1312, 1135, 763.
(2-(2-fluorophenyl)-2-tosylethyl)(phenyl)selane 3b
White solid. Mp: 93-94 oC; 1H NMR (400 MHz; CDCl3): δ = 2.35 (s, 3H), 3.66 (dd, J1 = 3.2 Hz, J2 = 14.8 Hz, 1H), 4.09 (q, J = 11.6 Hz, 1H), 4.84 (dd, J1 = 2.8 Hz, J2 = 11.6 Hz, 1H), 6.82-6.95 (m, 3H), 7.09-7.25 (m, 6H), 7.31-7.47 (m, 4H). 13C NMR (100 MHz; CDCl3): δ = 21.5, 33.1, 60.1, 115.5, 115.7, 124.0, 125.4, 125.5, 127.9, 128.8, 128.9, 129.0, 129.1, 129.2, 129.3, 129.5, 135.6, 144.5, 158.7, 161.2. HRMS (ESI-TOF) Calcd for C21H20FO2SSe, [M+H]+ 435.0333; Found 435.0337. IR (KBr, cm-1): 3066, 2979, 1492, 1313, 758.
(2-(2-chlorophenyl)-2-tosylethyl)(phenyl)selane 3c
White solid. Mp: 130-131 oC; 1H NMR (400 MHz; CDCl3): δ = 3.69 (s, 3H), 3.73 (d, J = 12.0 Hz, 1H), 4.08 (s, 1H), 5.06 (s, 1H), 6.91-6.99 (m, 5H), 7.005-7.69 (m, 3H), 7.23-7.48 (m, 5H). 13C NMR (100 MHz; CDCl3): δ = 21.5, 39.8, 60.4, 126.6, 128.0, 128.4, 128.8, 129.3, 129.5, 129.9, 133.3, 135.5, 135.5, 135.7, 144.4. HRMS (ESI-TOF) Calcd for C21H20ClO2SSe, [M+H]+ 451.0032; Found 451.0037. IR (KBr, cm-1): 3054, 1595, 1302, 1143, 743.
(2-(3-chlorophenyl)-2-tosylethyl)(phenyl)selane 3d
White solid. Mp: 151-153 oC; 1H NMR (400 MHz; CDCl3): δ = 2.36 (s, 3H), 3.63 (dd, J1 = 3.2 Hz, J2 = 14.8 Hz, 1H), 3.92 (q, J = 11.6 Hz, 1H), 4.62 (dd, J1 = 2.8 Hz, J2 = 11.6 Hz, 1H), 6.79-6.94 (m, 2H), 7.02-7.09 (m, 4H), 7.27-7.42 (m, 7H). 13C NMR (100 MHz; CDCl3): δ = 21.1, 21.5, 39.9, 61.2, 124.9, 127.9, 128.2, 128.4, 128.6, 129.3, 135.4, 136.2, 137.9, 144.1. HRMS (ESI-TOF) Calcd for C21H20ClO2SSe, [M+H]+ 451.0032; Found 451.0036. IR (KBr, cm-1): 3062, 2977, 1531, 1450, 735.
(2-(3-bromophenyl)-2-tosylethyl)(phenyl)selane 3e
White solid. Mp: 165-166 oC; 1H NMR (400 MHz; CDCl3): δ = 2.36 (s, 3H), 3.63 (dd, J1 = 3.2 Hz, J2 = 14.8 Hz, 1H), 3.92 (q, J = 11.6 Hz, 1H), 4.61 (dd, J1 = 2.8 Hz, J2 = 11.6 Hz, 1H), 6.91-7.09 (m, 5H), 7.28 (d, J = 5.2 Hz, 1H), 7.30-7.42 (m, 7H). 13C NMR (100 MHz; CDCl3): δ = 21.5, 39.1, 60.8, 122.4, 126.5, 127.7, 127.8, 129.0, 129.4, 129.5, 129.8, 130.4, 135.8, 135.9, 139.9, 144.6. HRMS (ESI-TOF) Calcd for C21H20BrO2SSe,, [M+H]+ 494.9534; Found 494.9538. IR (KBr, cm-1): 3066, 2917, 1307, 1135, 762.
(2-(4-fluorophenyl)-2-tosylethyl)(phenyl)selane 3f
White solid. Mp: 120-122 oC; 1H NMR (400 MHz; CDCl3): δ = 2.36 (s, 3H), 3.63 (dd, J1 = 3.2 Hz, J2 = 14.8 Hz, 1H), 3.93 (q, J = 12.0 Hz, 1H), 4.68 (dd, J1 = 3.2 Hz, J2 = 11.6 Hz, 1H), 6.77 (t, J = 8.8, 2 H), 6.99 (q, J = 5.2 Hz, 2H), 7.10 (d, J = 4.0 Hz, 2H), 7.26 (d, J = 7.6 Hz, 2H), 7.32-7.40 (m, 5H). 13C NMR (100 MHz; CDCl3): δ = 21.5, 38.9, 61.2, 115.2, 115.4, 127.9, 128.2, 128.8, 129.3, 129.4, 129.5, 133.6, 135.6, 136.2, 144.5, 160.7, 163.2. HRMS (ESI-TOF) Calcd for C21H20FO2SSe, [M+H]+ 435.0333; Found 435.0338. IR (KBr, cm-1): 3067, 2976, 1150, 1134, 547.
(2-(4-chlorophenyl)-2-tosylethyl)(phenyl)selane 3g
White solid. Mp: 115-117 oC; 1H NMR (400 MHz; CDCl3): δ = 2.36 (s, 3H), 3.65 (dd, J1 = 3.2 Hz, J2 = 14.8 Hz, 1H), 3.93 (q, J = 12.0 Hz, 1H), 4.64 (dd, J1 = 3.2 Hz, J2 = 11.6 Hz, 1H), 6.91 (d, J = 8.4, 2H), 7.01-7.09 (m, 4H), 7.25 (t, J = 7.6 Hz, 2H), 7.31-7.41 (m, 5H). 13C NMR (100 MHz; CDCl3): δ = 21.5, 39.1, 61.0, 127.9, 128.4, 128.9, 129.0, 129.4, 129.5, 133.3, 135.6, 136.0, 136.3, 144.6. HRMS (ESI-TOF) Calcd for C21H20ClO2SSe, [M+H]+ 451.0032; Found 451.0029. IR (KBr, cm-1): 3066, 2968, 1490, 1300, 1084, 686.
(2-(4-bromophenyl)-2-tosylethyl)(phenyl)selane 3h
White solid. Mp: 132-133 oC; 1H NMR (400 MHz; CDCl3): δ = 2.40 (s, 3H), 3.65 (dd, J1 = 2.4 Hz, J2 = 14.4 Hz, 1H), 3.88 (d, J = 12.4 Hz, 1H), 4.63 (t, J = 8.8 Hz, 1H), 6.84 (d, J = 7.6, 2H), 7.09-7.18 (m, 4H), 7.16 (d, J = 8.0 Hz, 2H), 7.27-7.42 (m, 5H). 13C NMR (100 MHz; CDCl3): δ = 21.6, 39.1, 61.0121.4, 127.8, 128.9, 129.2, 129.4, 129.5, 131.4, 135.6, 136.1, 136.8, 144.6. HRMS (ESI-TOF) Calcd for C21H20BrO2SSe, [M+H]+ 494.9534; Found 494.9537. IR (KBr, cm-1): 3070, 2976, 1402, 1313, 1135, 544.
(2-(4-nitrophenyl)-2-tosylethyl)(phenyl)selane 3i
White solid. Mp: 148-149 oC; 1H NMR (400 MHz; CDCl3): δ = 2.35 (s, 3H), 3.70 (dd, J1 = 2.4 Hz, J2 = 14.4 Hz, 1H), 3.95 (q, J = 12.0 Hz, 1H), 4.70 (dd, J1 = 3.2 Hz, J2 = 11.6 Hz, 1H), 7.10-7.27 (m, 5H), 7.34-7.43 (m, 5H), 7.64 (t, J = 6.8 Hz, 1H), 7.91 (d, J = 8.4 Hz, 2H). 13C NMR (100 MHz; CDCl3): δ = 21.5, 38.7, 60.5, 123.4, 124.2, 127.9, 128.4, 129.3, 129.5, 129.7, 130.2, 136.0, 145.1, 145.8, 146.8. HRMS (ESI-TOF) Calcd for C21H20NO4SSe, [M+H]+ 462.0278; Found 462.0275. IR (KBr, cm-1): 3074, 3051, 1534, 1422, 747, 735.
(2-(2,6-dichlorophenyl)-2-tosylethyl)(phenyl)selane 3j
White solid. Mp: 187-188 oC; 1H NMR (400 MHz; CDCl3): δ = 2.34 (s, 3H), 3.82 (dd, J1 = 4.0 Hz, J2 = 14.8 Hz, 1H), 4.77 (q, J = 12.0 Hz, 1H), 5.43 (dd, J1 = 3.6 Hz, J2 = 11.6 Hz, 1H), 6.98-7.11 (m, 4H), 7.19-7.21 (m, 3H), 7.24-7.53 (m, 5H). 13C NMR (100 MHz; CDCl3): δ = 21.5, 36.4, 59.3, 127.8, 128.5, 128.7, 128.8, 129.3, 129.4, 129.6, 134.8, 134.9, 135.1, 135.4, 135.5, 144.4. HRMS (ESI-TOF) Calcd for C21H19Cl2O2SSe, [M+H]+ 484.9648; Found 484.9642. IR (KBr, cm-1): 3078, 3002, 1437, 1149, 739.
phenyl(2-(m-tolyl)-2-tosylethyl)selane 3k
White solid. Mp: 116-117 oC; 1H NMR (400 MHz; CDCl3): δ = 2.13 (s, 3H), 3.32 (s, 3H), 3.63 (m, 1H), 4.02 (m, 1H), 4.67 (m, 1H), 6.72 (s, 1H), 6.90-7.05 (m, 4H), 7.26-7.44 (m, 8H). 13C NMR (100 MHz; CDCl3): δ = 21.1, 21.4, 39.9, 61.2, 124.9, 127.9, 128.1, 128.3, 128.4, 128.6, 129.3, 129.4, 135.4, 136.2, 137.9, 144.1. HRMS (ESI-TOF) Calcd for C22H23O2SSe, [M+H]+ 431.0582; Found 431.0587. IR (KBr, cm-1): 3063, 2977, 1596, 1308, 746.
phenyl(2-(m-tolyl)-2-tosylethyl)selane 3l
White solid. Mp: 107-109 oC; 1H NMR (400 MHz; CDCl3): δ = 2.27 (s, 3H), 2.36 (s, 3H), 3.61 (dd, J1 = 4.0 Hz, J2 = 14.8 Hz, 1H), 3.99 (q, J = 12.0 Hz, 1H), 4.67 (dd, J1 = 3.6 Hz, J2 = 11.6 Hz, 1H), 6.90-6.96 (m, 4H), 7.07 (d, J = 8.4 Hz, 2H), 7.27 (t, J = 7.6 Hz, 2H), 7.32-7.45 (m, 5H). 13C NMR (100 MHz; CDCl3): δ = 21.1, 21.5, 39.6, 61.3, 127.5, 127.9, 128.6, 128.7, 129.1, 129.4, 134.5, 135.2, 136.3, 137.4, 144.1. HRMS (ESI-TOF) Calcd for Calcd for C22H23O2SSe, [M+H]+ 431.0582; Found 431.0585. IR (KBr, cm-1): 3024, 2917, 1401, 1299, 763.
(2-(4-(tert-butyl)phenyl)-2-tosylethyl)(phenyl)selane 3m
White solid. Mp: 83-84 oC; 1H NMR (400 MHz; CDCl3): δ = 1.26 (s, 9H), 2.32 (s, 3H), 3.63 (dd, J1 = 4.0 Hz, J2 = 14.8 Hz, 1H), 4.04 (q, J = 12.0 Hz, 1H), 4.74 (dd, J1 = 3.6 Hz, J2 = 11.6 Hz, 1H), 6.94-7.08 (m, 6H), 7.29-7.47 (m, 7H). 13C NMR (100 MHz; CDCl3): δ = 21.5, 31.3, 34.4, 39.7, 61.3, 125.3, 127.3, 127.9, 128.6, 128.8, 129.3, 129.4, 134.2, 135.3, 136.4, 143.8, 150.6. HRMS (ESI-TOF) Calcd for C25H29O2SSe, [M+H]+ 473.1057; Found 473.1053. IR (KBr, cm-1): 3052, 2969, 1400, 1136, 739.
(2-(4-(chloromethyl)phenyl)-2-tosylethyl)(phenyl)selane 3n
White solid. Mp: 115-117 oC; 1H NMR (400 MHz; CDCl3): δ = 2.32 (s, 3H), 3.64 (dd, J1 = 3.2 Hz, J2 = 14.8 Hz, 1H), 3.96 (q, J = 11.6 Hz, 1H), 4.45 (s, 1H), 4.70 (dd, J1 = 3.6 Hz, J2 = 11.6 Hz, 1H), 6.95-7.07 (m, 6H), 7.24-7.41 (m, 7H). 13C NMR (100 MHz; CDCl3): δ = 21.5, 39.5, 45.6, 61.1, 127.8, 127.9, 128.2, 128.6, 128.8, 129.4, 129.5, 135.5, 136.1, 136.8, 138.0, 144.3. HRMS (ESI-TOF) Calcd for C22H22ClO2SSe, [M+H]+ 465.0197; Found 465.0192. IR (KBr, cm-1): 2957, 2924, 2854, 1436, 1311, 742.
(3-(2-chlorophenoxy)-2-tosylpropyl)(phenyl)selane 3o
White liquid. 1H NMR (400 MHz; CDCl3): δ = 2.37 (s, 3H), 3.51 (q, J = 4.0 Hz, 1H), 3.86 (q, J = 4.0 Hz, 1H), 4.04 (d, J = 4.8 Hz, 1H), 4.31 (d, J = 4.4 Hz, 1H), 4.45 (t, J = 6.0 Hz, 1H), 6.76-6.93 (m, 2H), 7.14-7.28 (m, 7H), 7.31-7.68 (m, 4H). 13C NMR (100 MHz; CDCl3): δ = 21.6, 35.8, 57.6, 69.5, 113.8, 122.1, 123.2, 127.5, 127.6, 127.7, 127.9, 128.4, 129.4, 129.9, 130.1, 130.2, 134.9, 136.1, 144.8, 153.5. HRMS (ESI-TOF) Calcd for C22H22ClO3SSe, [M+H]+ 481.0141; Found481.0146. IR (KBr, cm-1): 2360, 1589, 1400, 1302, 746.
(3-(4-chlorophenoxy)-2-tosylpropyl)(phenyl)selane 3p
White liquid. 1H NMR (400 MHz; CDCl3): δ = 2.42 (s, 3H), 3.45 (d, J = 11.2 Hz, 1H), 3.80 (t, J = 9.6 Hz, 2H), 4.25 (d, J = 6.4 Hz, 1H), 4.38 (d, J = 3.6 Hz, 1H), 6.75 (t, J = 9.2 Hz, 2H), 7.20-7.33 (m, 7H), 7.45 (d, J = 7.2 Hz, 2H), 7.67 (d, J = 8.0 Hz, 2H). 13C NMR (100 MHz; CDCl3): δ = 21.6, 35.7, 57.8, 68.9,126.0, 126.3, 127.3, 127.8, 128.4, 129.2, 129.4, 129.9, 135.0, 136.1, 144.9, 156.6. HRMS (ESI-TOF) Calcd for C22H22ClO3SSe, [M+H]+ 481.0141; Found481.0148. IR (KBr, cm-1): 3051, 2408, 1358, 1305, 753.
phenyl(3-(p-tolyloxy)-2-tosylpropyl)selane 3q
White liquid. 1H NMR (400 MHz; CDCl3): δ = 2.30 (s, 3H), 2.41 (s, 3H), 3.45 (dd, J1 = 2.4 Hz, J2 = 13.6 Hz, 1H), 3.81-3.86 (m, 2H), 4.25 (q, J = 4.4 Hz, 1H), 4.37 (t, J = 6.0 Hz, 1H), 6.72 (d, J = 8.8 Hz, 2H), 7.06 (d, J = 8.4 Hz, 2H), 7.22-7.32 (m ,5H), 7.46 (d, J = 6.8 Hz, 2H), 7.68 (d, J = 8.4 Hz, 2H). 13C NMR (100 MHz; CDCl3): δ = 20.5, 21.5, 57.9, 68.9, 114.6, 127.5, 127.8, 128.3, 129.3, 129.8, 129.9, 130.6, 134.9, 136.3, 144.7, 156.0. HRMS (ESI-TOF) Calcd for C23H25O3SSe, [M+H]+ 461.0690; Found 461.0697. IR (KBr, cm-1): 3056, 2970, 1487, 1453, 756, 734.
phenyl(2-phenyl-2-(phenylsulfonyl)ethyl)selane 3r
White solid. Mp: 93-95 oC; 1H NMR (400 MHz; CDCl3): δ = 3.69 (dd, J1 = 3.2 Hz, J2 = 13.6 Hz, 1H), 4.04 (q, J = 11.6 Hz, 1H), 4.72 (dd, J1 = 3.2 Hz, J2 = 13.6 Hz, 1H), 7.05-7.10 (m, 5H), 7.27-7.34 (m, 5H), 7.42-7.52 (m, 5H). 13C NMR (100 MHz; CDCl3): δ = 39.8, 61.1, 127.6, 127.7, 127.8, 128.4, 128.5, 128.7, 128.8, 129.4, 133.2, 135.4, 137.6, 139.3. HRMS (ESI-TOF) Calcd for C20H19O2SSe, [M+H]+ 403.0271; Found 403.0268. IR (KBr, cm-1): 3059, 2926, 1679, 1306, 743.
(2-((4-fluorophenyl)sulfonyl)-2-phenylethyl)(phenyl)selane 3s
White solid. Mp: 90-92 oC; 1H NMR (400 MHz; CDCl3): δ = 3.66 (dd, J1 = 3.2 Hz, J2 = 13.6 Hz, 1H), 4.02 (q, J = 11.6 Hz, 1H), 4.73 (dd, J1 = 3.2 Hz, J2 = 13.6 Hz, 1H), 6.89-7.11 (m, 7H), 7.28-7.49 (m, 7H). 13C NMR (100 MHz; CDCl3): δ = 39.8, 61.3, 115.9, 116.1, 127.6, 127.7, 128.5, 128.8, 129.1, 129.4, 130.7, 130.8, 135.5. HRMS (ESI-TOF) Calcd for C20H18FO2SSe, [M+H]+ 421.0177; Found 421.0173. IR (KBr, cm-1): 2954, 2924, 2854, 1447, 1135.
(4-methoxyphenyl)(2-phenyl-2-tosylethyl)selane 3t
White solid. Mp: 100-101 oC; 1H NMR (400 MHz; CDCl3): δ = 3.62 (q, J = 5.2 Hz, 1H), 3.80 (s, 3H), 4.36 (dd, J1 = 3.2 Hz, J2 = 10.4 Hz, 1H), 5.18 (d, J = 8.8 Hz, 1H), 6.86 (d, J = 7.2 Hz, 1H), 7.27-7.49 (m, 10H), 7.63 (d, J = 8.0 Hz, 1H). 13C NMR (100 MHz; CDCl3): δ = 21.1, 38.3, 57.6, 63.8, 120.1, 124.0, 124.4, 126.8, 127.4, 128.9, 129.0, 129.4, 132.9, 136.6, 138.0, 146.0. HRMS (ESI-TOF) Calcd for C22H22O3SSe, [M+H]+ 446.0453; Found 446.0459. IR (KBr, cm-1): 3065, 2954, 2857, 1453, 1305, 762.
(4-chlorophenyl)(2-phenyl-2-tosylethyl)selane 3u
White solid. Mp: 123-125 oC; 1H NMR (400 MHz; CDCl3): δ = 3.80 (q J = 8.0 Hz, 1H), 4.06 (q, J = 8.4 Hz, 1H), 5.29 (q, J = 6.8 Hz, 1H), 6.80 (d, J = 8.8 Hz, 2H), 7.23-7.32 (m, 10H), 7.43 (d, J = 8.4 Hz, 1H). 13C NMR (100 MHz; CDCl3): δ = 23.6, 38.7, 61.8, 120.1, 124.0, 124.4, 126.8, 127.4, 128.9, 129.0, 129.4, 136.6, 138.0, 146.0. HRMS (ESI-TOF) Calcd for C21H19ClO2SSe, [M+H]+ 449.9961; Found 449.9965. IR (KBr, cm-1): 3052, 2979, 1437, 1085, 763, 756.