M. Larsson et al. / Tetrahedron 60 (2004) 10659–10669
10667
1048, 1007, 948, 907, 846 cmK1. Anal. Calcd for C9H20OS:
C 61.3; H 11.4. Found: C 61.1; H 11.3.
897, 737, 690, 670 cmK1. Anal. Calcd for C14H22OS: C
70.5; H 9.3. Found: C 70.6; H 9.4.
3.4.10. 2-Methyl-1-(phenylsulfonyl)heptan-3-ol (sulfonyl
of 4). Oxidation of 4 was performed as above to give a
colourless oil after LC. Bp 260 8C/1.2 mbar (threo/erythro,
3.4.7. 2-Methyl-1-(phenylsulfanyl)pentan-3-ol (3). Entry
1, Table 3; threo/erythro, 3T/3E, 65/35. LC furnished a
colourless oil. Bp 140 8C/0.5 mbar. H NMR: d 0.91–0.99
1
1
70/30). H NMR: d 0.85–0.92 (3H, m), 1.02 (0.9H, d, JZ
(3H, m), 1.00 (1.05H, d, JZ6.7 Hz), 1.05 (1.95H, d, JZ
6.9 Hz), 1.33–1.67 (3H, m), 1.75–1.90 (1H, m), 2.80
(0.65H, dd, JZ8.4, 12.8 Hz), 2.85 (0.35H, dd, JZ7.1,
13.0 Hz), 3.10 (0.35H, dd, JZ6.9, 12.8 Hz), 3.23 (0.65H,
dd, JZ4.2, 12.7 Hz), 3.44–3.51 (0.65H, m), 3.66–3.73
(0.35H, m), 7.13–7.37 (5H, m). 13C NMR (asterisk denotes
minor diastereomer peaks): d 10.0, 10.6*, 13.1*, 15.9, 26.9,
27.4*, 36.9, 37.4*, 37.8*, 38.4, 74.8*, 76.5, 125.7, 128.8
(2C), 128.9 (2C), 137.1. MS (EI): m/z 210 (100) (MC), 193
(28), 163 (8), 123 (25), 110 (32), 100 (30). IR: 3406, 3058,
2964, 2932, 2876, 1584, 1480, 1458, 1438, 1378, 1302,
1272, 1245, 1186, 1091, 1069, 1026, 972, 897, 738,
690 cmK1. Anal. Calcd for C12H18OS: C 68.5; H 8.6.
Found: C 68.5; H 8.8.
7.0 Hz), 1.15 (2.1H, d, JZ6.9 Hz), 1.18–1.48 (6H, m), 1.82
(1H, br s, OH), 2.06–2.21 (0.7H, m), 2.25–2.34 (0.3H, m),
2.90–3.01 (1H, m), 3.33–3.46 (1.7H, m), 3.73–3.79 (0.3H,
m), 7.53–7.69 (3H, m), 7.91–7.95 (2H, m). 13C NMR
(asterisk denotes minor diastereomer peaks): d 13.7*, 14.0,
17.4, 22.6, 27.7, 28.3*, 33.3*, 33.7*, 34.1, 34.5, 58.5, 59.5*,
73.3*, 75.0, 127.8 (2C), 129.3 (2C), 133.6, 140.0. MS (EI):
m/z 271 (7) (MCH)C, 253 (11), 228 (10), 213 (12), 170 (4),
156 (7), 143 (42), 125 (23), 87 (48), 78 (40), 69 (100). IR:
3510, 3066, 2957, 2933, 2872, 1466, 1459, 1448, 1406,
1381, 1304, 1147, 1086, 999, 986, 749, 689 cmK1. Anal.
Calcd for C14H22O3S: C 62.2; H 8.2. Found: C 62.5; H 8.1.
3.4.11. 3-[(Phenylsulfanyl)methyl]hexan-2-ol (6a, R1Z
C2H5, R2ZMe). Entry 1, Table 2; threo/erythro, 6aT/6aE,
95/05. LC furnished a colourless oil. 1H NMR: d 0.90 (3H, t,
JZ6.9 Hz), 1.20 (3H, d, JZ6.3 Hz), 1.17–1.55 (4H, m),
1.61–1.71 (1H, m), 1.71 (1H, s, –OH), 2.86–3.15 (2H, m),
3.94 (0.95H, app. quint, JZ6.2 Hz), 4.02–4.16 (0.05H, m),
7.13–7.37 (5H, m). 13C NMR (asterisk denotes minor
diastereomer peaks): d 14.3, 15.3*, 19.7, 20.2, 20.6, 31.3*,
31.8, 34.5, 34.7*, 43.9*, 44.5, 68.8*, 69.1, 125.8, 128.9 (2C),
129.0 (2C), 137.1. MS (EI): m/z 224 (100) (MC), 207 (20),
123 (27), 110 (50), 85 (15).
3.4.8. 2-Methyl-1-(phenylsulfonyl)pentan-3-ol (sulfonyl
of 3). m-Chloroperbenzoic acid (0.57 g, 2.54 mmol) was
added to a solution of 3 (0.21 g, 1.01 mmol) in CH2Cl2
(7 mL) at 0 8C. The mixture was allowed to reach room
temperature over night, NaHCO3 (10 mL, sat. aq.) was
added and the aqueous phase was extracted with Et2O (3!
15 mL) and the combined Et2O extract was washed with
NaHCO3 (15 mL, sat. aq.), brine (15 mL), dried (Na2SO4),
filtered and the solvent was evaporated off, furnishing a
yellowish oil (0.20 g, 81%) after LC (EtOAc gradient in
cyclohexane), 99% pure by GC. Bp 235 8C/0.6 mbar.
(threo/erythro, 65/35). 1H NMR: d 0.91 (1.95H, t, JZ
7.4 Hz), 0.94 (1.05H, t, JZ7.4 Hz), 1.02 (1.05H, d, JZ
7.0 Hz), 1.14 (1.95H, d, JZ6.9 Hz), 1.27–1.57 (2H, m),
1.85 (1H, br s, OH), 2.09–2.20 (0.65H, m), 2.26–2.35
(0.35H, m), 2.94 (0.65H, dd, JZ8.5, 14.2 Hz), 2.97 (0.35H,
dd, JZ6.9, 14.1 Hz), 3.32–3.47 (1.65H, m), 3.65–3.71
(0.35H, m), 7.53–7.69 (3H, m), 7.91–7.95 (2H, m). 13C
NMR (asterisk denotes minor diastereomer peaks): d 9.79,
10.6*, 13.6*, 17.4, 26.5*, 27.2, 33.4*, 34.1, 58.6, 59.6*,
74.8*, 76.4, 127.8 (2C), 129.3 (2C), 133.6, 140.0. MS (EI):
m/z 243 (34) (MCH)C, 225 (32), 213 (12), 200 (30), 182
(7), 143 (75), 125 (43), 100 (19), 78 (100), 59 (90). The 1H
NMR and 13C NMR spectral data were similar to those
reported in the literature for the erythro-isomer.12
3.4.12. 4-[(Phenylsulfanyl)methyl]heptan-3-ol (7a, R1Z
C2H5, R2ZEt). Entry 1, Table 5; threo/erythro, 7aT/7aE,
87/13. LC furnished a colourless oil. Bp 190 8C/2.8 mbar.
1H NMR: d 0.90 (3H, t, JZ7.0 Hz), 0.95 (3H, t, JZ7.2 Hz),
1.27–1.62 (6H, m), 1.64 (1H, s, –OH), 1.67–1.77 (1H, m),
2.98 (1H, dd, JZ6.5, 12.6 Hz), 3.12 (1H, dd, JZ5.0,
12.6 Hz), 3.62 (0.87H, dt, JZ4.5, 8.4 Hz), 3.78 (0.13H, dt,
JZ3.2, 6.6 Hz), 7.13–7.37 (5H, m). 13C NMR (asterisk
denotes minor diastereomer peaks): d 10.4, 10.8*, 14.3,
20.2, 20.7*, 26.8*, 27.3, 30.7*, 32.2, 34.3, 35.2*, 42.4*, 42.6,
74.3*, 74.5, 125.8, 128.9 (2C), 129.0 (2C), 137.2. MS (EI):
m/z 308 (100) (MC), 291 (28), 249 (12), 169 (65), 123 (53),
110 (82). MS (EI): m/z 238 (100) (MC), 221 (58), 123 (5),
110 (8). IR: 3416, 3059, 2959, 2931, 2872, 1584, 1480,
1464, 1438, 1378, 1304, 1090, 1069, 1026, 998, 973, 738,
690 cmK1. Anal. Calcd for C14H22OS: C 70.5; H 9.3.
Found: C 70.5; H 9.5.
3.4.9. 2-Methyl-1-(phenylsulfanyl)heptan-3-ol (4). Entry
3, Table 3; threo/erythro, 4T/4E, 70/30. LC furnished a
colourless oil. Bp 180 8C/0.9 mbar. H NMR: d 0.88–0.93
1
3.4.13. 4-[(Phenylsulfanyl)methyl]nonan-5-ol (8a, R1Z
C2H5, R2Zn-Bu). Entry 2, Table 5; threo/erythro, 8aT/
8aE, 87/13. LC furnished a colourless oil. Bp 195 8C/
(3H, m), 1.00 (0.9H, d, JZ6.9 Hz), 1.05 (2.1H, d, JZ
6.9 Hz), 1.23–1.58 (7H, m), 1.74–1.88 (1H, m), 2.79 (0.7H,
dd, JZ8.4, 12.7 Hz), 2.84 (0.3H, dd, JZ7.1, 12.9 Hz), 3.10
(0.3H, dd, JZ6.9, 12.8 Hz), 3.22 (0.7H, dd, JZ4.3,
12.7 Hz), 3.51–3.58 (0.7H, m), 3.74–3.79 (0.3H, m), 7.12–
7.37 (5H, m). 13C NMR (asterisk denotes minor dia-
stereomer peaks): d 13.2*, 14.1, 15.9, 22.7*, 22.7, 28.0,
28.4*, 33.7, 34.2*, 36.9, 37.7*, 38.7, 73.3*, 75.1, 125.7,
128.9 (4C), 137.1. MS (EI): m/z 238 (100) (MC), 221 (14),
163 (15), 151 (14), 128 (34), 123 (57), 110 (100), 86 (88), 69
(49), 58 (47). IR: 3406, 3059, 2957, 2932, 2871, 1584, 1481,
1466, 1458, 1438, 1378, 1272, 1115, 1090, 1026, 1001, 978,
1
0.3 mbar. H NMR: d 0.90 (6H, t, JZ7.0 Hz), 1.21–1.55
(10H, m), 1.61 (1H, s, –OH), 1.63–1.75 (1H, m), 2.97 (1H,
dd, JZ6.5, 12.6 Hz), 3.10 (1H, dd, JZ5.0, 12.6 Hz), 3.70
(0.87H, dt, JZ4.6, 7.6 Hz), 3.83–3.90 (0.13H, m), 7.13–
7.37 (5H, m). 13C NMR (asterisk denotes minor dia-
stereomer peaks): d 14.1, 14.3, 20.3, 20.7*, 22.7, 28.3, 28.5*,
30.7*, 32.2, 33.6*, 34.1, 34.3, 35.2*, 42.8*, 43.0, 72.7*, 73.0,
125.8, 128.9 (2C), 129.0 (2C), 137.2. MS (EI): m/z 266
(100) (MC), 249 (73), 123 (5), 110 (11). IR: 3422, 3059,
2957, 2931, 2871, 1584, 1480, 1466, 1458, 1438, 1378,