Helvetica Chimica Acta Vol. 86 (2003)
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1171, 933. 1H-NMR (300 Hz, CDCl3): 7.84 7.76 (m, 2 H); 7.65 7.60 (m, 2 H); 7.54 7.47 (m, 1 H); 7.40 7.32 (m,
2 H); 7.17 7.10 (m, 2 H); 7.04 6.97 (m, 4 H); 5.55 (d, J 7.2, 1 H); 3.05 2.91 (m, 1 H); 2.90 2.80 (m, 2 H);
2.79 2.71 (m, 2 H); 2.35 (s, 3 H). 13C-NMR (75.5 MHz, CDCl3): 194.7 (CO); 145.0, 141.3, 141.2, 134.5, 132.8
(arom. Cq); 133.8, 129.6, 128.7, 128.6, 128.0, 126.6, 126.5, 124.4, 124.3 (arom. CH); 82.8 (CH); 42.0 (CH); 34.9
(CH2); 34.7 (CH2); 21.6 (Me). EI-MS: 290 (19), 234 (3, [M À TsOH] ), 155 (17, Ts ), 135 (100), 115 (14), 105
(62, PhCO ), 91 (37, PhCH2 ), 77 (42, Ph ), 65 (12), 51 (9). Anal. calc. for C24H22O4S (406.50): C 70.91, H 5.46,
S 7.89; found: C 70.49, H 5.65, S 7.74.
1-Cyclohexyl-2-oxo-2-phenylethyl 4-Methylbenzene-1-sulfonate (3n). GP D starting from 7i afforded 3n in
88% yield. Colorless solid. M.p. 64 678. IR (KBr): 2932, 2853, 1689, 1597, 1449, 1366, 1172, 939. 1H-NMR
(300 MHz, CDCl3): 7.81 7.73 (m, 2 H); 7.66 7.59 (m, 2 H); 7.54 7.46 (m, 1 H); 7.41 7.32 (m, 2 H); 7.17 7.10
(m, 2 H); 5.28 (d, J 5.9, 1 H); 2.30 (s, 3 H); 1.96 1.80 (m, 1 H); 1.78 1.35 (m, 5 H); 1.20 0.93 (m, 5 H).
13C-NMR (75.5 MHz, CDCl3): 195.1 (CO); 144.8, 134.8, 133.0 (arom. Cq); 133.6, 129.6, 128.6, 128.0 (arom.
CH); 85.1 (CH); 40.5 (CH); 28.9 (CH2); 27.8 (CH2); 25.7 (2 CH2); 25.5 (CH2); 21.6 (Me). EI-MS: 200 (5, [M À
TsOH] ), 155 (22, Ts ), 105 (100, PhCO ), 95 (53), 91 (41, PhCH2 ), 77 (38, Ph ), 65 (12), 51 (7). Anal. calc.
for C21H24O4S (372.48): C 67.72, H 6.49, S 8.61; found: C 67.40, H 6.22, S 8.43.
trans-1-[4-(tert-Butyl)cyclohexyl]-2-oxo-2-phenylethyl 4-Methylbenzene-1-sulfonate (3o). GP D starting
from 7j afforded 3o in 87% yield. Colorless solid. M.p. 97 998. IR (KBr): 2935, 2857, 1678, 1597, 1449, 1367,
1172, 941. 1H-NMR (300 MHz, CDCl3): 7.83 7.75 (m, 2 H); 7.67 7.60 (m, 2 H); 7.56 7.47 (m, 1 H); 7.40 7.31
(m, 2 H); 7.18 7.10 (m, 2 H); 5.68 (d, J 6.2, 1 H); 2.31 (s, 3 H); 2.00 1.86 (m, 1 H); 1.82 1.66 (m, 3 H); 1.63
1.52 (m, 1 H); 1.35 1.08 (m, 2 H); 1.02 0.80 (m, 3 H); 0.70 (s, 9 H). 13C-NMR (75.5 MHz, CDCl3): 196.2
(CO); 144.8, 134.5, 132.4 (arom. Cq); 133.6, 129.6, 128.5, 128.3, 128.0 (arom. CH); 85.1 (CH); 47.4 (CH); 40.6
(CH); 32.4 (Cq); 29.3 (CH2); 27.4 (3 Me); 26.6 (CH2); 26.5 (CH2); 21.6 (CH2); 21.6 (Me). Anal. calc. for
C25H32O4S (428.59): C 70.06, H 7.53, S 7.48; found: C 69.91, H 7.49, S 7.58.
2-Oxo-2-phenyl-1-(3,4,5,6-tetrahydro-2H-pyran-4-yl)ethyl 4-Methylbenzene-1-sulfonate (3p). GP D start-
ing from 7k afforded 3p in 84% yield. Colorless solid. M.p. 139 1418. IR (KBr): 2954, 2857, 1697, 1596, 1449,
1369, 1237, 1210, 1181, 1090, 1071, 1009, 949, 934, 918, 876, 851, 718. 1H-NMR (300 MHz, CDCl3): 7.82 7.77 (m,
2 H); 7.66 7.60 (m, 2 H); 7.57 7.49 (m, 1 H); 7.44 7.35 (m, 2 H); 7.18 7.12 (m, 2 H); 5.29 (d, J 6.8, 2 H);
3.92 3.79 (m, 2 H); 3.26 3.15 (m, 2 H); 2.32 (s, 3 H); 2.20 2.08 (m, 1 H); 1.63 1.21 (m, 4 H). 13C-NMR
(75.5 MHz, CDCl3): 194.6 (CO); 145.1, 134.7, 132.8 (arom. Cq); 133.9, 129.7, 128.7, 128.5, 128.1 (arom. CH);
83.8 (CH); 67.3 (CH2); 67.0 (CH2); 38.0 (CH); 28.6 (CH2); 28.0 (CH2); 21.6 (Me). EI-MS: 374 (1, M ), 269 (18),
202 (10, [M À TsOH] ), 155 (60, Ts ), 105 (100, PhCO ), 91 (44, PhCH2 ), 77 (34, Ph ). Anal. calc. for
C20H22O5S (374.45): C 64.15, H 5.92, S 8.56; found: C 63.94, H 5.98, S 8.72.
1-{1-[(4-Methylphenyl)sulfonyl]piperidin-4-yl}-2-oxo-2-phenylethyl 4-Methylbenzene-1-sulfonate (3q). GP
D starting from 7l afforded 3q in 81% yield. Colorless solid. M.p. 97 998. IR (KBr): 1691, 1597, 1448, 1357, 1338,
1163, 933. 1H-NMR (300 MHz, CDCl3): 7.76 7.69 (m, 2 H); 7.65 7.58 (m, 2 H); 7.54 7.45 (m, 2 H); 7.40 7.31
(m, 1 H); 7.24 7.12 (m, 2 H); 5.25 (d, J 6.4, 1 H); 3.75 3.60 (m, 2 H); 2.33 (s, 3 H); 2.32 (s, 3 H); 2.11 1.96
(m, 2 H); 1.85 1.62 (m, 2 H); 1.53 1.28 (m, 3 H). 13C-NMR (75.5 MHz, CDCl3): 194.3 (CO); 145.3, 143.6,
134.5, 132.8, 132.6 (arom. Cq); 134.0, 129.8, 129.6, 128.8, 128.6, 128.0, 127.6 (arom. CH); 83.0 (CH); 45.7 (CH2);
45.6 (CH2); 38.1 (CH); 27.4 (CH2); 26.6 (CH2); 21.6 (CH3); 21.5 (Me). EI-MS: 355 (7, [M À TsOH] ), 200 (60),
155 (26, Ts ), 105 (100, PhCO ), 91 (81, PhCH2 ), 82 (37), 77 (30, Ph ), 65 (19), 42 (10). Anal. calc. for
C27H29NO6S2 (527.65): C 61.46, H 5.54, N 2.65, S 12.15; found: C 61.34, H 5.55, N 2.87, S 12.25.
1-{1-[(tert-Butoxy)carbonyl]piperidin-4-yl}-2-oxo-2-phenylethyl 4-Methylbenzene-1-sulfonate (3r). GP D
starting from 7m afforded 3r in 87% yield. Colorless solid. M.p. 123 1248. IR (KBr): 1688, 1594, 1401, 1362,
1171, 925. 1H-NMR (300 MHz, CDCl3): 7.81 7.75 (m, 2 H); 7.65 7.59 (m, 2 H); 7.56 7.49 (m, 1 H); 7.43 7.34
(m, 2 H); 7.18 7.11 (m, 2 H); 5.30 (d, J 6.4, 1 H); 4.11 3.90 (m, 2 H); 2.59 2.43 (m, 2 H); 2.31 (s, 3 H);
2.10 1.96 (m, 1 H); 1.72 1.61 (m, 1 H); 1.35 (s, 9 H); 1.40 1.14 (m, 3 H). 13C-NMR (75.5 MHz, CDCl3): 194.6,
154.4 (CO); 145.1, 134.6, 132.7 (arom. Cq); 133.9, 129.7, 128.7, 128.6, 128.0 (arom. CH); 83.6 (Cq); 43.6 (br.,
CH2); 43.1(br., CH2); 39.0 (CH); 28.3 (3 Me); 27.9 (CH2); 27.1 (CH2); 21.6 (Me). EI-MS: 301 (2, [M À
TsOH] ), 245 (16), 201 (15), 160 (16), 140 (13), 105 (100, PhCO ), 96 (25), 91 (36, PhCH2 ), 82 (76), 77 (49,
Ph ), 57 (93), 41 (65). Anal. calc. for C25H31NO6S (473.58): C 63.40, H 6.60, N 2.96, S 6.77; found: C 63.64,
H 6.62, N 3.17, S 6.37.
Methyl 3-Bromo-2-methyl-4-oxo-4-phenylbutanoate (4a). GP E starting from 1f afforded 4a in 100% yield
(mixture of diastereoisomers, ds 55 :45; the data of the minor product are given in square brackets). Yellow-
brown oil. IR (film): 1742, 1699, 1646, 1285, 1261, 858. 1H-NMR (300 MHz, CDCl3): 8.06 8.00 (m, 2 H); 7.65
7.56 (m, 1 H); 7.54 7.45 (m, 2 H); 5.32 [5.34] (d, J 9.8 [10.2], 1 H); 3.65 [3.78] (s, 3 H); 3.43 3.32 [3.54 3.45]
(m, 1 H); 1.53 [1.26] (d, J 7.2 [6.8], 3 H). 13C-NMR (75.5 MHz, CDCl3): 193.1 [191.6], 174.1 [173.9] (CO);