ˇ
L. Rehová, I. Císarˇová, U. Jahn
FULL PAPER
25.81 (d), 38.2 (t), 38.7 (t), 61.6 (d), 69.7 (d), 127.9 (d), 128.3 (d),
129.8 (d), 131.3 (d), 134.1 (d), 134.9 (d), 135.9 (s), 144.1 (s) ppm.
691 cm–1. MS (ESI+): m/z (%) = 341 (100) [M + Na+], 199 (20) [M
+ Na+ – PhSO2H], 165 (20) [PhSO2H + Na+]. C18H22O3S (318.43):
1
calcd. C 67.89, H 6.96, S 10.07; found C 67.91, H 7.11, S 9.89. H
2,6-Dimethylhept-4-yl 2-(1-Hydroxy-3-phenylpropyl)phenyl Sulfone
NMR (400 MHz, CDCl3): δ = 0.58 (t, J = 7.4 Hz, 3 H), 1.12 (t, J
= 7.5 Hz, 3 H), 1.47 (dq, J = 7.5, 15.0 Hz, 1 H), 1.72 (dq, J = 7.4,
15.0 Hz, 1 H), 1.96 (dq, J = 7.5, 15.1 Hz, 1 H), 2.21 (dq, J = 7.5,
15.1 Hz, 1 H), 4.19 (d, J = 2.5 Hz, 1 H), 4.92 (d, J = 2.5 Hz, 1 H),
7.22 (m, 5 H), 7.54 (m, 2 H), 7.65 (m, 1 H), 7.90 (m, 2 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 8.5 (q), 9.4 (q), 19.5 (t), 24.0 (t),
74.1 (d), 76.1 (s), 128.1 (d), 128.38 (d), 128.41 (d), 129.0 (d), 130.2
(d), 133.9 (d), 137.5 (s), 139.1 (s) ppm.
(13d): Yield 374 mg (93%) as a colorless oil. Rf (EtOAc/hexane,
1:5) = 0.35. IR: ν = 3498, 2957, 1468, 1454, 1331, 1295, 1140, 1115,
˜
1058, 747, 725 cm–1. MS (ESI+): m/z (%) = 425 (100) [M + Na+].
C24H34O3S (402.59): calcd. C 71.60, H 8.51, S 7.96; found C 71.43,
H 8.55, S 7.77. 1H NMR (400 MHz, CDCl3): δ = 0.73 (d, J =
6.4 Hz, 3 H), 0.82 (d, J = 6.4 Hz, 3 H), 0.87 (d, J = 6.4 Hz, 3 H),
0.92 (d, J = 6.4 Hz, 3 H), 1.41 (m, 2 H), 1.57 (m, 1 H), 1.62–1.86
(m, 3 H), 2.13 (m, 1 H), 2.27 (m, 1 H), 2.75 (m, 1 H), 3.00 (m, 2
H), 3.15 (m, 1 H), 5.46 (m, 1 H), 7.25 (m, 5 H), 7.47 (m, 1 H), 7.65
(m, 1 H), 7.75 (m, 1 H), 7.99 (m, 1 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 21.9 (q), 22.1 (q), 22.8 (q), 22.9 (q), 25.5 (d), 25.6 (d),
32.8 (t), 38.2 (t), 38.5 (t), 39.4 (t), 61.5 (d), 69.2 (d), 126.0 (d), 128.1
(d), 128.5 (d), 128.7 (d, 2 C), 131.2 (d), 133.4 (d), 135.7 (s), 141.5
(s), 144.9 (s) ppm.
1-(4-Bromophenyl)-2-ethyl-2-(phenylsulfonyl)butan-1-ol (14b): Yield
129 mg (65%) as colorless crystals, m.p. 119–121 °C. Rf (EtOAc/
hexane, 1:5) = 0.22. IR: ν = 3487, 2981, 2940, 1485, 1446, 1281,
˜
1144, 1073, 1010, 725, 690 cm–1. MS (ESI+): m/z (%) = 419/417
(100/100) [M + Na+], 165 (40) [PhSO2H + Na+]. C18H21BrO3S
(396.33): calcd. C 54.41, H 5.33, S 8.07, Br 20.11; found C 54.41,
H 5.33, S 7.98, Br 20.21. 1H NMR (400 MHz, CDCl3): δ = 0.67 (t,
J = 7.4 Hz, 3 H), 1.10 (t, J = 7.5 Hz, 3 H), 1.53 (dq, J = 7.4,
14.8 Hz, 1 H), 1.69 (dq, J = 7.4, 14.8 Hz, 1 H), 1.92 (dq, J = 7.5,
15.0 Hz, 1 H), 2.16 (dq, J = 7.5, 15.0 Hz, 1 H), 4.32 (d, J = 2.5 Hz,
1 H), 4.90 (d, J = 2.5 Hz, 1 H), 7.15 (m, 2 H), 7.39 (m, 2 H), 7.56
(m, 2 H), 7.67 (m, 1 H), 7.90 (m, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 8.7 (q), 9.5 (q), 19.8 (t), 24.1 (t), 73.9 (d), 75.8 (s),
122.0 (s), 129.1 (d), 130.2 (d), 130.3 (d), 131.3 (d), 134.1 (d), 137.4
(s), 138.3 (s) ppm.
2,6-Dimethylhept-4-yl 2-(1-Hydroxycyclohexyl)phenyl Sulfone (13e):
Yield 312 mg (85%) as a colorless oil. Rf (EtOAc/hexane, 1:5) =
0.44. IR: ν = 3495, 2955, 2930, 1468, 1386, 1288, 1267, 1133, 1112,
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994, 768, 745 cm–1. MS (ESI+): m/z (%) = 389 (30) [M + Na+], 349
(100) [M – OH–], 223 (20) [M + H+ – OH – CH(iBu)2]. C21H34O3S
(366.56): calcd. C 68.81, H 9.35, S 8.75; found C 68.87, H 9.23, S
1
8.97. H NMR (400 MHz, CDCl3): δ = 0.70 (d, J = 6.2 Hz, 6 H),
0.78 (d, J = 6.2 Hz, 6 H), 1.32 (m, 2 H), 1.54 (m, 4 H), 1.65–1.89
(m, 10 H), 4.21 (m, 1 H), 4.53 (s, 1 H), 7.30 (ddd, J = 8.1, 6.7,
1.8 Hz, 1 H), 7.48 (m, 2 H), 8.07 (dd, J = 8.1, 1.2 Hz, 1 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 21.9 (t), 22.3 (q), 23.0 (q), 25.7
(t), 25.9 (d, 2 C), 38.8 (t, 2 C), 40.1 (t), 61.9 (d), 75.3 (s), 126.7 (d),
129.2 (d), 133.1 (d), 133.2 (d), 136.7 (s), 152.2 (s) ppm.
4-Ethyl-2-methyl-4-(phenylsulfonyl)hexan-3-ol (14c): Yield 100 mg
(70%) as colorless crystals, m.p. 90–91 °C. Rf (EtOAc/hexane, 1:5)
= 0.29. IR: ν = 3515, 2966, 2886, 1446, 1278, 1120, 1073, 1016,
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758, 721, 690 cm–1. MS (ESI+): m/z (%) = 307 (100) [M + Na+],
165 (40) [PhSO2H + Na+]. C15H24O3S (284.41): calcd. C 63.34, H
8.51, S 11.27; found C 63.53, H 8.48, S 11.25. 1H NMR (400 MHz,
CDCl3): δ = 0.91 (2ϫt, J = 7.5 Hz, 6 H), 1.04 (2ϫd, J = 6.6 Hz, 6
H), 1.54 (dq, J = 7.5, 14.8 Hz, 1 H), 1.83 (dq, J = 7.5, 15.1 Hz, 1
H), 2.03 (dq, J = 7.5, 14.8 Hz, 2 H), 2.21 (m, 1 H), 3.19 (d, J =
7.8 Hz, 1 H), 3.80 (dd, J = 3.0, 7.8 Hz, 1 H), 7.51 (m, 2 H), 7.61
(m, 1 H), 7.87 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
8.9 (q), 9.1 (q), 17.6 (q), 23.3 (t), 24.3 (q), 24.9 (t), 29.5 (d), 74.4
(s), 77.8 (d), 128.9 (d), 130.2 (d), 133.8 (d), 138.8 (s) ppm.
2,6-Dimethylhept-4-yl 2-(1-Hydroxy-1-phenylbenzyl)phenyl Sulfone
(13f): Yield 424 mg (94%) as colorless crystals, m.p. 112–113 °C.
R (EtOAc/hexane, 1:5) = 0.59. IR: ν = 3403, 2955, 1467, 1441,
˜
f
1383, 1291, 1167, 1113, 1072, 1043, 956, 765, 748 cm–1. MS (ESI+):
m/z (%) = 473 (100) [M + Na+], 329 (40) [M + Na+ – OH –
CH(iBu)2], 307 (30) [M + H+ – OH – CH(iBu)2]. HRMS (ESI+):
m/z [M + Na+] calcd. for C28H34O3SNa+: 473.2121, found
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473.2120. H NMR (400 MHz, CDCl3): δ = 0.74 (d, J = 6.6 Hz, 6
H), 0.87 (d, J = 6.6 Hz, 6 H), 1.35 (m, 2 H), 1.52 (m, 2 H), 1.74
(m, 2 H), 3.75 (m, 1 H), 6.30 (s, 1 H), 6.88 (dd, J = 7.9, 1.3 Hz, 1
H), 7.08 (m, 4 H), 7.23 (m, 6 H), 7.35 (td, J = 7.9, 1.5 Hz, 1 H),
7.41 (td, J = 7.9, 1.3 Hz, 1 H), 8.14 (dd, J = 7.9, 1.5 Hz, 1 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 22.3 (q), 23.1 (q), 25.8 (d, 2 C),
38.4 (t), 38.5 (t), 62.6 (d), 83.4 (s), 127.6 (d), 127.7 (d), 128.1 (d),
128.2 (d), 132.4 (d), 133.7 (d), 134.0 (d), 137.2 (s), 147.4 (s), 148.2
(s) ppm.
(E)-3-Ethyl-3-(phenylsulfonyl)oct-5-en-4-ol (14d): Yield 96 mg
(64%) as colorless crystals, m.p. 65–66 °C. Rf (EtOAc/hexane, 1:5)
= 0.32. IR: ν = 3493, 2969, 2939, 1446, 1281, 1131, 1075, 971, 721,
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691, 604 cm–1. MS (ESI+): m/z (%) = 319 (100) [M + Na+], 165
(30) [PhSO2H + Na+]. C16H24O3S (296.42): calcd. C 64.83, H 8.16,
S 10.82; found C 64.94, H 8.24, S 10.52. 1H NMR (400 MHz,
CDCl3): δ = 0.96 (m, 9 H), 1.61 (dq, J = 7.4, 14.8 Hz, 1 H), 1.80
(dq, J = 7.5, 15.1 Hz, 1 H), 1.94 (m, 4 H), 3.47 (d, J = 6.1 Hz, 1
H), 4.34 (t, J = 6.1 Hz, 1 H), 5.55 (ddt, J = 1.4, 6.2, 15.2 Hz, 1 H),
5.71 (dtd, J = 0.8, 7.1, 15.2 Hz, 1 H), 7.50 (m, 2 H), 7.60 (m, 1 H),
7.86 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 8.5 (q), 8.8
(q), 13.3 (q), 22.0 (t), 23.6 (t), 25.5 (t), 73.4 (s), 74.8 (d), 126.7 (d),
128.8 (d), 130.4 (d), 133.8 (d), 136.9 (d), 138.3 (s) ppm.
(2-Hydroxyalkyl) Phenyl Sulfones 14a–e (General Procedure):
nBuLi (0.41 mL, 0.65 mmol, 1.6 m in hexane) was added dropwise
to a stirred solution of sulfone 7k (106 mg, 0.5 mmol) and TMEDA
(0.15 mL, 0.98 mmol) in dry THF (4 mL) at –78 °C under a nitro-
gen atmosphere. After stirring for 10 min, the aldehyde (0.7 mmol)
in THF (2 mL) was added dropwise at –78 °C. The reaction mix-
ture was warmed to 0 °C, stirred at this temperature for 1 h until
complete as indicated by TLC and quenched with water. The layers
were separated and the aqueous was extracted with diethyl ether
(3ϫ 20 mL). The combined organic extracts were washed with
brine, dried with MgSO4, filtered and the solvents evaporated. Puri-
fication by column chromatography (EtOAc/hexane, 1:50) gave
sulfones 14a–e.
(E)-4-Ethyl-1-phenyl-4-(phenylsulfonyl)hex-1-en-3-ol (14e): Yield
122 mg (71%) as colorless crystals, m.p. 85–86 °C. Rf (EtOAc/hex-
ane, 1:5) = 0.20. IR: ν = 3491, 2974, 2943, 2886, 1446, 1361, 1279,
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1133, 1073, 969, 755, 721, 690, 604 cm–1. MS (ESI+): m/z (%) =
367 (100) [M + Na+], 327 (10) [M – OH–]. C20H24O3S (344.15):
1
calcd. C 69.73, H 7.02, S 9.31; found C 69.67, H 6.89, S 9.13. H
NMR (400 MHz, CDCl3): δ = 1.05 (m, 6 H), 1.77 (dq, J = 7.4,
15.0 Hz, 1 H), 1.88 (dq, J = 7.6, 15.1 Hz, 1 H), 2.04 (m, 2 H), 3.69
(d, J = 6.6 Hz, 1 H), 4.56 (td, J = 1.3, 6.6 Hz, 1 H), 6.28 (dd, J =
6.6, 15.8 Hz, 1 H), 6.64 (dd, J = 1.3, 15.8 Hz, 1 H), 7.27 (m, 5 H),
2-Ethyl-1-phenyl-2-(phenylsulfonyl)butan-1-ol (14a): Yield 127 mg
(80%) as colorless crystals, m.p. 119–121 °C. Rf (EtOAc/hexane,
1:5) = 0.30. IR: ν = 3488, 2975, 2943, 1447, 1281, 1143, 1073, 722,
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Eur. J. Org. Chem. 2014, 1461–1476