10.1002/hlca.201900140
Helvetica Chimica Acta
HELVETICA
organic layer was saturated with brine, dried over anhydrous sodium sulfate,
filtered and evaporated to dryness. The target compound 3 was finally
obtained by column chromatography using the adequate petroleum ether:
ethyl acetate mixture as the eluent.
chromatography on silica gel (Pentane/EtOAc), affording 3h (115 mg, 75%)
as a single diastereromer and as a white solid. Rf = 0.42 (Pentane/EtOAc
95:5). IR (ATR) νmax (cm‐1) = 2955, 2926, 1621, 1444, 1316, 1306, 1142, 828,
610, 556. 1H‐NMR (300 MHz, CDCl3): δ (ppm) = 7.91 ‐ 7.81 (m, 2H), 7.66 ‐ 7.48
(m, 3H), 6.85 (dd, J = 15.1, 9.7 Hz, 1H), 6.27 (dd, J = 15.1, 0.5 Hz, 1H), 2.13
(ddd, J = 21.8, 10.3, 3.5 Hz, 1H), 1.81 ‐ 1.51 (m, 5H), 1.44 ‐ 0.90 (m, 5H), 0.87
(dd, J = 6.7, 1.2 Hz, 6H), 0.66 (d, J = 6.9 Hz, 3H). 13C‐NMR (75.5 MHz, CDCl3):
δ (ppm) = 151.7, 141.1, 133.3, 129.4, 129.3, 127.5, 47.2, 44.0, 41.2, 34.8, 32.2,
29.0, 24.2, 22.5, 21.3, 15.6. HRMS (ESI): [M+Na]+ calculated for C16H26O2SNa
329.1546: found 329.1545.
(E)‐((2‐cyclohexylvinyl)sulfonyl)benzene (3a) and Diphenylsulfone
(4).
Synthesized according to the general procedure from iodocyclohexane 1a
(105 mg, 0.5 mmol, 1eq.), (E)‐1,2‐bis(phenylsulfonyl)ethene 2 (308.37 mg, 1
mmol, 2 eq.), diphenyliodonium hexafluorophosphate (640.2 mg, 1.5 mmol,
3 eq.) and triethylamine (140 μL, 1 mmol, 2 eq) in dry DMF (0.2 M, 2.5 mL).
The reaction was stirred for 15 h. The crude mixture was purified by
chromatography on silica gel (Pentane/EtOAc 9:1), affording 3a (101 mg,
80%) as a colorless oil and diphenylsulfone 4 (60 mg, 55%) as a white solid.
Rf = 0.43 (Pentane/EtOAc 90:10). IR (ATR) νmax (cm‐1) = 2927, 2852, 1622,
1446, 1318, 1306, 1146, 1086, 973. 1H‐NMR (300 MHz, CDCl3): δ (ppm) = 7.90
– 7.77 (m, 2H), 7.61 – 7.40 (m, 3H), 6.94 (dd, J = 15.2, 6.4 Hz, 1H), 6.24 (dd, J
= 15.2, 1.5 Hz, 1H), 2.23 – 2.06 (m, 1H), 1.82 – 1.50 (m, 5H), 1.41 – 1.03 (m,
5H). 13C‐NMR (75.5 MHz, CDCl3): δ (ppm) = 151.74, 140.77, 133.10, 129.15,
128.24, 127.45, 39.82, 31.21, 25.66, 25.48. HRMS (ESI): [M+H]+ calculated for
C14H19O2S 251.1100. found 251.1105. Diphenylsulfone (4). Rf = 0.38
(PE/EtOAc 90:10). IR (ATR), νmax (cm‐1) = 3081, 3065, 1448, 1309, 1296, 1154,
761, 728, 699, 689. 1H‐NMR (300 MHz, CDCl3): δ (ppm) = 8.08 – 7.75 (m, 4H),
7.60 – 7.40 (m, 6H). 13C‐NMR (75.5 MHz, CDCl3): δ (ppm) = 141.52, 133.13,
129.21, 127.57. HRMS (ESI): [M+Na]+ calculated for C12H10O2SNa 241.0293.
found 241.0291.
Diphenyliodonium hexafluorophosphate mediated alkenylation of
1‐iodohexane. (E)‐((6‐oct‐1‐en‐1‐yl)sulfonyl)benzene (3k) and
Hexylsulfonylbenzene (5).
Synthesized according to the general procedure from 1‐iodohexane 1k (74
μL, 0.5 mmol, 1 eq.), (E)‐1,2‐bis(phenylsulfonyl)ethene 2 (308.37 mg, 1
mmol, 2 eq.), diphenyliodonium hexafluorophosphate (320 mg, 0.75 mmol,
1.5 eq.) and triethylamine (140 μL, 1 mmol, 2 eq) in dry DMF (0.2 M, 2.5 mL).
The reaction was stirred for 24 h. The crude mixture was purified by
chromatography on silica gel (PE/EtOAc), affording 3k (32 mg, 25%) as a
colorless oil and hexylsulfonyl‐benzene 5 (43 mg, 38%) as a colorless oil.
(E)‐(oct‐1‐en‐1‐ylsulfonyl)benzene (3k). Rf = 0.45 (PE/EtOAc 95:5). IR (ATR)
ν
max (cm‐1) = 2928, 2857, 1625, 1446, 1319, 1307, 1146, 1086, 821, 594. 1H‐
NMR (300 MHz, CDCl3): δ (ppm) = 7.92 – 7.81 (m, 2H), 7.66 – 7.47 (m, 3H),
6.99 (dt, J = 15.1, 6.8 Hz, 1H), 6.30 (dt, J = 15.1, 1.6 Hz, 1H), 2.28 – 2.14 (m,
2H), 1.49 – 1.40 (m, 2H), 1.31 – 1.21 (m, 6H), 0.89 – 0.81 (m, 3H). 13C‐NMR
(75.5 MHz, CDCl3): δ (ppm) = 147.34, 140.77, 133.16, 130.26, 129.18, 127.51,
31.48, 31.41, 28.66, 27.52, 22.44, 13.96. HRMS (ESI): [M+H]+ calculated for
C14H21O2S 253.1256. found 253.1260. Hexylsulfonylbenzene (5). Rf = 0.25
(PE/EtOAc 95:5). IR (ATR), νmax (cm‐1) = 2931, 2859, 1447, 1305, 1146, 1086,
742, 689, 534. 1H‐NMR (300 MHz, CDCl3): δ (ppm) = 7.95 – 7.85 (m, 2H), 7.69
– 7.50 (m, 3H), 3.18 – 2.84 (m, 2H), 1.78 – 1.61 (m, 2H), 1.43 – 1.26 (m, 2H),
1.27 – 1.23 (m, 4H), 0.87 – 0.81 (m, 3H). 13C‐NMR (75.5 MHz, CDCl3): δ (ppm)
= 139.17, 133.55, 129.19, 127.99, 56.28, 31.10, 27.89, 22.55, 22.22, 13.85.
HRMS (ESI): [M+Na]+calculated for C12H18O2SNa 249.0919. found 249.0925.
1‐((E)‐2‐(Phenylsulfonyl)vinyl)adamantane (3b).
Synthesized according to the general procedure from 1‐iodoadamantane
1b (131 mg, 0.5 mmol, 1eq.), (E)‐1,2‐bis(phenylsulfonyl)ethene 2 (308.37 mg,
1 mmol, 2 eq.), diphenyliodonium hexafluorophosphate (640.2 mg, 1.5
mmol, 3 eq.) and triethylamine (140 μL, 1 mmol, 2 eq) in dry DMF (0.2 M,
2.5 mL). The reaction was stirred for 15 h. The crude mixture was purified
by chromatography on silica gel (PE/EtOAc 9:1), affording 3b (98.5 mg,
65%) as a colorless oil. Rf = 0.32 (PE/EtOAc 90:10). IR (ATR), νmax (cm‐1) =
2905, 2848, 2666, 1616, 1446, 1321, 1303, 1149. 1H‐NMR (300 MHz, CDCl3):
δ (ppm) = 7.90 ‐ 7.82 (m, 2H), 7.64 ‐ 7.46 (m, 3H), 6.83 (d, J = 15.3 Hz, 1H),
6.13 (d, J = 15.3 Hz, 1H), 2.00 (s, 3H), 1.79 ‐ 1.54 (m, 12H). 13C‐NMR (75.5 MHz,
CDCl3): δ (ppm) = 156.2, 141.0, 133.2, 129.3, 127.6, 126.5, 40.8, 36.4, 36.2,
27.9. HRMS(ESI):[M+H]+ calculated for C18H23O2S303.1413. found303.1415.
Supplementary Material
Synthetic procedures and spectroscopic data are reported in the electronic
Supporting information available on the WWW under
http://dx.doi.org/10.1002/MS‐number.
(E)‐((2‐(2‐Isopropyl‐5‐methylcyclohexyl)vinyl)sulfonyl)benzene
(3i).
Synthesized according to the general procedure from (1S,2R,4R)‐2‐iodo‐1‐
isopropyl‐4‐ methylcyclohexane‐2‐iodooctane 1i (133 mg, 0.5 mmol, 1 eq.),
(E)‐1,2‐bis(phenylsulfonyl)ethene
2 (308.37 mg, 1 mmol, 2 eq.),
Acknowledgements
diphenyliodonium hexafluorophosphate (640.2 mg, 1.5 mmol, 3 eq.) and
triethylamine (140 μL, 1 mmol, 2 eq) in dry DMF (0.2 M, 2.5 mL). The
reaction was stirred for 15 h. The crude mixture was purified by
G.K. thanks the University of Ankara for post‐doctoral funding. AC
acknowledge the government of Tunisia for a mobility grant and the
4
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