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J. Yu et al. / Tetrahedron: Asymmetry 22 (2011) 2039–2055
4.3.7. 1-Oxo-1-phenylbutan-2-yl 4-methylbenzenesulfonate 25
7.07 (t, J = 4.0 Hz, 1H), 7.20 (d, J = 8.0 Hz, 2H), 7.63 (d, J = 4.0 Hz,
1H), 7.69 (d, J = 8.0 Hz, 2H), 7.80 (d, J = 4.0 Hz, 1H); 13C NMR
(100 MHz): d = 19.03, 21.60, 78.43, 127.98, 128.38, 129.78,
133.13, 133.75, 135.19, 139.83, 145.17, 187.90; IR (KBr): 3094,
2921, 2850, 1702, 1684, 1597, 1575, 1437, 1413, 1370, 1306,
1263, 1245, 1190, 1177, 1073, 1018, 945, 892, 852, 809, 748,
666 cmꢂ1; HRMS (ESI): m/z calcd for C14H14O4S2Na [M+Na]+:
333.0226, found: 333.0231; HPLC conditions: Chiracel AD column,
hexane/2-propanol, 90:10, 0.6 mL/min, 210 nm, tR = 29.0 min
(minor), 33.4 min (major).
Colorless solid, mp: 80–82 °C; ½a D25
ꢁ
¼ ꢂ8:2 (c 0.9, CHCl3); 1H
NMR (300 MHz, CDCl3): d = 0.90 (t, J = 7.2 Hz, 3H), 1.84–1.90 (m,
2H), 2.31 (s, 3H), 5.49 (dd, J = 5.4, 7.8 Hz, 1H), 7.16 (d, J = 8.1 Hz,
2H), 7.36 (t, J = 7.8 Hz, 2H), 7.50 (t, J = 7.5 Hz, 1H), 7.66 (d,
J = 8.1 Hz, 2H), 7.77 (d, J = 7. 2 Hz, 2H); 13C NMR (75 MHz):
d = 9.49, 21.56, 26.18, 82.47, 127.96, 128.58, 128.67, 129.65,
133.22, 133.71, 133.76, 144.92, 194.85; HPLC conditions: Chiracel
AD column, hexane/2-propanol, 90:10, 0.7 mL/min, 220 nm,
tR = 20.7 min (minor), 23.9 min (major).
4.3.8. 1-Oxo-1-phenylpentan-2-yl 4-methylbenzenesulfonate 26
Colorless solid, mp: 62–63 °C; 1H NMR (400 MHz, CDCl3):
d = 0.81 (t, J = 7.2 Hz, 3H), 1.31–1.44 (m, 2H), 1.75–1.85 (m, 2H),
2.32 (s, 3H), 5.52–5.56 (dd, J = 4.5, 8.4 Hz, 1H), 7.16 (d, J = 8.1 Hz,
2H), 7.37 (t, J = 7.5 Hz, 2H), 7.51 (t, J = 7.2 Hz, 1H), 7.66 (d,
J = 8.4 Hz, 2H), 7.77 (d, J = 7.2 Hz, 2H); 13C NMR (100 MHz):
d = 13.30, 18.38, 21.57, 34.67, 81.13, 128.00, 128.61, 128.68,
129.65, 133.26, 133.68, 134.11, 144.90, 195.00; IR (KBr): 2962,
2931, 2875, 1701, 1597, 1449, 1363, 1190, 1176, 1095, 941, 891,
815, 776, 697, 666, 578 cmꢂ1; HRMS (ESI): m/z calcd for C18H20O4S-
Na [M+Na]+: 355.0975, found: 355.0978; HPLC conditions: Chiracel
AD column, hexane/2-propanol, 88:12, 0.8 mL/min, 220 nm,
tR = 14.7 min (minor), 16.6 min (major).
4.3.13. 1-Oxo-1,2,3,4-tetrahydronaphthalen-2-yl 4-
methylbenzenesulfonate 31
Colorless oil; 1H NMR (400 MHz, CDCl3): d = 2.33–2.40 (m, 4H),
2.47–2.52 (m, 1H), 3.04–3.08 (m, 2H), 5.10 (dd, J = 4.8, 10.4 Hz, 1H),
7.17–7.30 (m, 4H), 7.44 (t, J = 7.6 Hz, 1H), 7.84–7.90 (m, 3H); 13C
NMR (100 MHz): d = 21.69, 27.34, 30.56, 80.09, 127.08, 128.01,
128.08, 128.64, 129.72, 131.14, 133.59, 134.23, 142.86, 144.89,
190.48; HPLC conditions: Chiracel AD column, hexane/2-propanol,
90:10, 0.6 mL/min, 220 nm. tR = 37.0 min (major), 39.2 min
(minor).
4.3.14. 2-Oxocyclohexyl 4-methylbenzenesulfonate 32
Colorless solid, mp: 72–74 °C; 1H NMR (400 MHz, CDCl3):
d = 1.64–1.73 (m, 2H), 1.85–1.98 (m, 3H), 2.30–2.34 (m, 2H), 2.44
(s, 3H), 2.52–2.56 (m, 1H), 4.88–4.92 (dd, J = 6.0, 10.8 Hz, 1H),
7.34 (d, J = 7.6 Hz, 2H), 7.83 (d, J = 7.6 Hz, 2H); 13C NMR
(100 MHz): d = 21.62, 23.08, 26.83, 34.52, 40.53, 81.79, 127.83,
129.67, 133.52, 144.86, 202.74; HPLC conditions: Chiracel AD col-
umn, hexane/2-propanol, 90:10, 0.6 mL/min, 220 nm, tR = 35.0 min
(minor), 43.1 min (major).
4.3.9. 2-Oxo-1,2-diphenylethyl 4-methylbenzenesulfonate 27
Colorless solid, mp: 104–105 °C; ½a D25
ꢁ
¼ ꢂ33:0 (c 1.0, CHCl3); 1H
NMR (400 MHz, CDCl3): d = 2.31 (s, 3H), 6.60 (s, 1H), 7.14 (d,
J = 8.0 Hz, 2H), 7.21–7.22 (m, 3H), 7.28–7.32 (m, 4H), 7.44 (t,
J = 7.6 Hz, 1H), 7.64 (d, J = 8.0 Hz, 2H), 7.76 (d, J = 8.0 Hz, 2H); 13C
NMR (100 MHz): d = 21.60, 82.23, 127.96, 128.11, 128.62, 128.93,
129.06, 129.60, 132.59, 133.46, 133.70, 133.92, 144.87, 191.97;
HPLC conditions: Chiracel AD column, hexane/2-propanol, 90:10,
0.6 mL/min, 220 nm, tR = 55.7 min (minor), 68.3 min (major).
4.3.10. 1-(Naphthalen-2-yl)-1-oxopropan-2-yl 4-
methylbenzenesulfonate 28
4.3.15. 1-Cyclohexyl-1-oxopropan-2-yl 4-
methylbenzenesulfonate 33
Colorless oil; 1H NMR (300 MHz, CDCl3): d = 1.49 (d, J = 6.9 Hz,
3H), 2.19 (s, 3H), 5.73 (q, J = 6.9 Hz, 1H), 7.04 (d, J = 8.1 Hz, 2H),
7.32–7.43 (m, 3H), 7.59 (d, J = 8.1 Hz, 2H), 7.66–7.75 (m, 2H), 7.86
(d, J = 8.1 Hz, 1H), 8.11–8.14 (m, 1H); 13C NMR (75 MHz): d = 18.33,
21.43, 78.72, 124.08, 125.07, 126.59, 127.51, 127.63, 127.98,
128.35, 129.60, 130.21, 132.42, 133.06, 133.35, 133.73, 144.79,
198.23; HPLC conditions: Chiracel AD column, hexane/2-propanol,
90:10, 0.6 mL/min, 220 nm; tR = 32.2 min (major), 33.9 min (minor).
Colorless solid, mp: 74–75 °C; ½a D25
¼ ꢂ7:75 (c 0.8, CHCl3);
ꢁ
1H NMR (400 MHz, CDCl3): d = 1.15–1.31 (m, 8H), 1.56–1.68
(m, 5H), 2.38 (s, 3H), 2.59–2.60 (m, 1H), 4.85–4.90 (m, 1H),
7.29 (d, J = 8.0 Hz, 2H), 7.72–7.75 (m, 2H); 13C NMR
(100 MHz): d = 17.70, 21.66, 25.30, 25.52, 25.60, 27.86, 28.64,
46.03, 79.57, 127.85, 129.91, 133.51, 145.16, 209.09; IR (KBr):
2932, 2856, 1718, 1598, 1450, 1368, 1190, 1178, 1097, 1015,
935, 914, 865, 826, 817, 790, 666, 567, 554 cmꢂ1
(ESI): m/z calcd for
16H22O4SNa [M+Na]+: 333.1131, found:
; HRMS
C
4.3.11. 1-(Furan-2-yl)-1-oxopropan-2-yl 4-
methylbenzenesulfonate 29
333.1132; HPLC conditions: Chiracel AD column, hexane/2-pro-
panol, 90:10, 0.6 mL/min, 254 nm, tR = 13.9 min (minor),
14.7 min (major).
Colorless oil; 1H NMR (400 MHz, CDCl3): d = 1.49 (d, J = 6.8 Hz,
3H), 2.36 (s, 3H), 5.45 (q, J = 6.8 Hz, 1H), 6.50–6.51 (m, 1H), 7.24
(d, J = 8.0 Hz, 2H), 7.30 (d, J = 7.6 Hz, 1H), 7.55 (s, 1H), 7.72 (d,
J = 8.0 Hz, 2H); 13C NMR (100 MHz): d = 18.43, 21.65, 77.35,
112.66, 120.08, 127.97, 129.80, 133.25, 145.12, 147.44, 149.51,
183.37; IR (KBr): 3367, 3137, 3068, 2990, 2925, 1794, 1742,
1688, 1590, 1569, 1464, 1367, 1190, 1178, 1122, 1015, 933, 892,
880, 816, 784, 752, 667, 574, 554 cmꢂ1; HRMS (ESI): m/z calcd
for C14H14O5SNa [M+Na]+: 317.0454, found: 317.0462; HPLC con-
ditions: Chiracel AD column, hexane/2-propanol, 90:10, 0.6 mL/
min, 220 nm; tR = 34.2 min (minor), 36.3 min (major).
4.3.16. 4,4-Dimethyl-3-oxopentan-2-yl 4-
methylbenzenesulfonate 34
Colorless oil; 1H NMR (300 MHz, CDCl3): d = 1.14 (s, 9H),
1.40 (d, J = 6.6 Hz, 3H), 2.44 (s, 3H), 5.42 (q, J = 6.6 Hz, 1H),
7.34 (d, J = 8.1 Hz, 2H), 7.79 (d, J = 8.1 Hz, 2H); 13C NMR
(75 MHz): d = 18.75, 21.62, 26.36, 43.74, 75.05, 127.84, 129.76,
133.86, 144.93, 209.36; IR (KBr): 2987, 2961, 2937, 1928,
1727, 1656, 1482, 1455, 1380, 1353, 1308, 1291, 1189,
1176, 1152, 989, 922, 819, 740, 665, 553, 528 cmꢂ1; HRMS
(ESI): m/z calcd for C14H24O4SN [M+NH4]+: 302.1421, found:
302.1421; HPLC conditions: Chiracel AD column, hexane/2-
propanol, 97:3, 0.5 mL/min, 220 nm; tR = 24.4 min (minor),
25.4 min (major).
4.3.12. 1-Oxo-1-(thiophen-2-yl)propan-2-yl 4-
methylbenzenesulfonate 30
Colorless solid, mp: 106–107 °C; 1H NMR (400 MHz, CDCl3):
d = 1.52 (d, J = 6.8 Hz, 3H), 2.34 (s, 3H), 5.38 (q, J = 6.8 Hz, 1H),