C.-G. Yang et al. / Tetrahedron: Asymmetry 13 (2002) 383–394
389
added followed by K2OsO2(OH)4 (14.8 mg, 0.08 mmol).
The reaction mixture was stirred for 3 h at this temper-
ature and quenched with saturated aqueous sodium
sulfite (15 mL). After stirring was continued for 1 h at
room temperature, the two phase was separated, and
the aqueous phase was extracted with ethyl acetate
(2×20 mL). The combined organic phases were washed
with brine (40 mL), dried over anhydrous sodium sul-
fate, and concentrated to afford the crude product,
which was purified by flash chromatography (silica,
hex/EtOAc, 4:1) to provide 10a–13a and 10b–13b.
(ddd, J=14.33 and 7.13 and 3.57 Hz, 1H), 3.36 (m,
1H), 3.29 (br, 1H), 2.33 (s, 3H), 145 (s, 9H); 13C NMR
(CDCl3, 100 MHz) l 157.0, 144.9, 135.3, 135.0, 129.8,
128.6, 126.8, 124.8, 123.3, 123.2, 120.1, 113.6, 80.0,
68.0, 46.8, 28.3, 21.4; EIMS m/z: 430. Anal. calcd for
C22H26N2O5S: C, 61.39; H, 6.05; N, 6.51. Found: C,
61.30; H, 5.97; N, 6.26%.
4.4.5. 1,1-Dimethylethyl (1S)-N-[1-[5-methoxyl-1-[(4-
methylphenyl)sulfonyl]-1H-indol-3-yl]-2-hydroxy]ethyl-
carbamate 12a. Mp 69–71°C (CH2Cl2/hexane); [h]2D0=
1
+22 (c 0.85, CHCl3); IR (KBr) 1693 cm−1; H NMR
4.4.1.
1,1-Dimethylethyl
(1S)-N-[1-[6-bromo-1-[(4-
(CDCl3, 300 MHz) l 7.85 (d, J=8.9 Hz, 1H), 7.72 (d,
J=8.2 Hz, 2H), 7.51 (s, 1H), 7.20 (d, J=8.0 Hz, 2H),
6.98 (d, J=2.1 Hz, 1H), 6.93 (dd, J=8.9 and 2.1 Hz,
1H), 5.12 (br d, J=7.6 Hz, 1H), 5.02 (br, 1H), 3.95 (br
s, 1H), 3.79 (s, 3H), 2.40 (s, 3H), 1.44 (s, 9H); 13C
NMR (CDCl3, 100 MHz) l 156.4, 155.9, 144.9, 135.0,
130.2, 129.8, 126.7, 124.2, 121.0, 114.6, 114.2, 102.0,
80.1, 64.8, 55.6, 49.1, 28.3, 21.5; ESIMS m/z: 483.2.
Anal. calcd for C23H28N2O6S: C, 60.00; H, 6.09; N,
6.09. Found: C, 60.00; H, 5.77; N, 6.29%.
methylphenyl)sulfonyl]-1H-indol-3-yl]-2-hydroxy]ethyl-
carbamate 10a. Mp 80–82°C (CH2Cl2/hexane); [h]2D01=
+47 (c 0.38, CHCl3); IR (KBr) 3405, 1693 cm−1; H
NMR (CDCl3, 300 MHz) l 8.15 (d, J=1.4 Hz, 1H),
7.76 (d, J=8.4 Hz, 2H), 7.54 (d, J=0.8 Hz, 1H), 7.43
(d, J=8.4 Hz, 1H), 7.33 (dd, J=8.4 and 1.7 Hz, 1H),
7.25 (d, J=8.4 Hz, 2H), 5.05 (m, 2H), 3.96 (m, 2H),
2.37 (s, 3H), 2.18 (br, 1H), 1.44 (s, 9H); 13C NMR
(CDCl3, 75 MHz) l 155.8, 145.4, 135.9, 134.9, 130.1,
128.0, 126.8, 126.7, 124.1, 121.0, 118.8, 116.8, 80.3,
64.8, 49.2, 28.3, 21.6; ESIMS m/z: 531.0/533.1. Anal.
calcd for C22H25BrN2O5S: C, 51.87; H, 4.91; N, 5.50.
Found: C, 52.07; H, 5.12; N, 5.31%.
4.4.6. 1,1-Dimethylethyl (1S)-N-[2-[5-methoxyl-1-[(4-
methylphenyl)sulfonyl]-1H-indol-3-yl]-2-hydroxy]ethyl-
carbamate 12b. Syrup; [h]2D0=+2.5 (c 1.675, CHCl3); IR
1
(KBr) 1695 cm−1; H NMR (CDCl3, 300 MHz) l 7.86
4.4.2.
1,1-Dimethylethyl
(1S)-N-[2-[6-bromo-1-[(4-
(dd, J=9.1 and 0.6 Hz, 1H), 7.72 (dd, J=8.5 and 1.8
Hz, 2H), 7.52 (s, 1H), 7.20 (d, J=8.0 Hz, 2H), 7.04 (d,
J=2.4 Hz, 1H), 6.92 (dd, J=9.1 and 2.4 Hz, 1H), 5.01
(br d, J=4.2 Hz, 1H), 4.95 (br, 1H), 3.80 (s, 3H), 3.60
(ddd, J=13.75 and 6.11 and 2.65 Hz, 1H), 3.37 (m,
1H), 3.28 (br, 1H), 2.33 (s, 3H), 1.45 (s, 9H); 13C NMR
(CDCl3, 100 MHz) l 157.0, 156.3, 144.9, 135.0, 130.1,
129.8, 129.6, 126.7, 124.0, 123.3, 114.6, 113.8, 102.7,
80.0, 68.1, 55.7, 46.6, 28.3, 21.5; ESIMS m/z: 483.1.
Anal. calcd for C23H28N2O6S: C, 60.00; H, 6.09; N,
6.09. Found: C, 60.10; H, 6.44; N, 5.77%.
methylphenyl)sulfonyl]-1H-indol-3-yl]-2-hydroxy]ethyl-
carbamate 10b. Syrup; [h]2D0=+9 (c 0.30, CHCl3); IR
(KBr) 3419, 1690 cm−1; H NMR (CDCl3, 300 MHz) l
1
8.16 (d, J=1.7 Hz, 1H), 7.76 (d, J=8.1 Hz, 2H), 7.53
(s, 1H), 7.48 (d, J=8.4 Hz, 1H), 7.34 (dd, J=8.4 and
1.7 Hz, 1H), 7.25 (d, J=8.4 Hz, 2H), 5.03 (m, 1H), 4.94
(br, 1H), 3.59 (ddd, J=13.82 and 6.53 and 2.71 Hz,
1H), 3.33 (m, 1H), 2.36 (s, 3H), 1.45 (s, 9 H); 13C NMR
(CDCl3, 75 MHz) l 157.1, 145.4, 136.0, 134.9, 130.1,
127.5, 127.0, 126.6, 123.6, 123.2, 121.4, 118.6, 116.8,
80.2, 68.1, 47.0, 28.3, 21.6; EIMS m/z: 509/511. Anal.
calcd for C22H25BrN2O5S: C, 51.87; H, 4.91; N, 5.50.
Found: C, 51.90; H, 5.11; N, 5.38%.
4.4.7.
1,1-Dimethylethyl
(1S)-N-[1-[5-bromo-1-[(4-
methylphenyl)sulfonyl]-1H-indol-3-yl]-2-hydroxy]ethyl-
carbamate 13a. Mp 81–82°C (CH2Cl2/hexane); [h]2D0=
4.4.3. 1,1-Dimethylethyl (1S)-N-[1-[(4-methylphenyl)-
sulfonyl-1H-indol-3-yl]-2-hydroxy]ethylcarbamate 11a.
Mp 74–75°C (CH2Cl2/hexane); [h]2D0=+38.6 (c 1.25,
+7.8 (c 1.90, CHCl3); IR (KBr) 1696 cm−1; H NMR
1
(CDCl3, 300 MHz) l 7.84 (d, J=9.2 Hz, 1H), 7.73 (d,
J=8.5 Hz, 2H), 7.70 (d, J=1.8 Hz, 1H), 7.57 (s, 1H),
7.41 (dd, J=9.2 and 1.8 Hz, 1H), 7.23 (d, J=8.5 Hz,
2H), 5.16 (br d, J=6.7 Hz, 1H), 4.99 (br, 1H), 3.96 (br
s, 2H), 2.28 (s, 3H), 1.46 (s, 9H); 13C NMR (CDCl3,
100 MHz) l 156.7, 146.3, 135.6, 134.7, 131.7, 130.8,
128.7, 127.6, 125.6, 123.4, 121.2, 117.7, 115.8, 80.9,
65.1, 49.4, 28.5, 21.7; ESIMS m/z: 531.1/533.1. Anal.
calcd for C22H25N2O5BrS: C, 51.87; H, 4.91; N, 5.50.
Found: C, 52.11; H, 5.20; N, 5.21%.
1
CHCl3); IR (KBr) 1694 cm−1; H NMR (CDCl3, 300
MHz) l 7.98 (d, J=8.2 Hz, 1H), 7.76 (dd, J=8.4 and
1.6 Hz, 2H), 7.56 (s, 1H), 7.55 (d, J=6.9 Hz, 1H),
7.36–7.20 (m, 4H), 5.13 (d, J=7.8 Hz, 1H), 5.06 (br,
1H), 3.96 (br, 2H), 2.34 (s, 3H), 145 (s, 9H); 13C NMR
(CDCl3, 75 MHz) l 155.7, 144.8, 134.9, 134.7, 129.6,
128.9, 126.5, 124.7, 123.4, 123.1, 120.8, 119.5, 113.4,
79.8, 64.4, 49.1, 28.0, 21.2; ESIMS m/z: 453.1. Anal.
calcd for C22H26N2O5S: C, 61.39; H, 6.05; N, 6.51.
Found: C, 61.26; H, 6.25; N, 6.20%.
4.4.8.
1,1-Dimethylethyl
(1S)-N-[2-[5-bromo-1-[(4-
4.4.4. 1,1-Dimethylethyl (1S)-N-[2-[(4-methylphenyl)-
sulfonyl-1H-indol-3-yl]-2-hydroxy]ethylcarbamate 11b.
Syrup; [h]2D0=+11.8 (c 1.20, CHCl3); IR (KBr) 1694
methylphenyl)sulfonyl]-1H-indol-3-yl]-2-hydroxy]ethyl-
carbamate 13b. Syrup; [h]2D0=+4.8 (c 1.50, CHCl3); IR
(KBr) 1694 cm−1; H NMR (CDCl3, 300 MHz) l 7.83
1
1
cm−1; H NMR (CDCl3, 300 MHz) l 7.98 (d, J=8.3
(d, J=9.2 Hz, 1H), 7.73 (d, J=8.5 Hz, 2H), 7.74 (s,
1H), 7.57 (s, 1H), 7.40 (dd, J=9.2 and 1.8 Hz, 1H),
7.22 (d, J=8.0 Hz, 2H), 5.02 (br s, 2H), 3.72 (br, 1H),
3.56 (ddd, J=14.05 and 6.72 and 3.66 Hz, 1H), 3.40
Hz, 1H), 7.76 (dd, J=8.4 and 1.7 Hz, 2H), 7.60 (d,
J=7.8 Hz, 1H), 7.58 (s, 1H), 7.32–7.25 (m, 2H), 7.21
(d, J=8.4 Hz, 2H), 5.06 (m, 1H), 4.95 (br, 1H), 3.62