Ghorai et al.
JOCArticle
1104, 1077, 1041, 1015, 968, 913, 876, 778, 757, 737, 704, 621,
3.07-3.16 (m, 2H), 5.00 (dd, J = 17.2, 1.5, Hz, 1H), 5.12 (dd,
J = 10.1, 1.2 Hz, 1H), 5.33 (d, J = 6.3 Hz, 1H), 5.73-5.82 (m,
1H), 5.85 (br s, 1H), 7.22-7.38 (m, 5H); 13C NMR (125 MHz,
CDCl3) δ 28.4, 44.4, 63.9, 80.0, 119.6, 128.1, 128.7, 129.2, 129.3,
129.6, 136.7, 154.9, 203.9.
1
595, 510; H NMR (CDCl3, 400 MHz) δ 1.34 (s, 9H), 1.82-
1.90 (m, 1H), 2.14-2.20 (m, 1H), 3.89-3.91 (br m, 1H), 4.60 (br
s, 1H), 4.99-5.11 (m, 2H), 5.36 (br s, 1H), 5.68-5.78 (m, 1H),
7.21-7.31 (m, 5H); 13C NMR (125 MHz, CDCl3) δ 28.4,
38.7, 58.7, 73.3, 79.8, 118.5, 126.7, 127.8, 128.0, 128.6, 134.3,
155.5.
(S)-tert-Butyl 2-Oxo-1-phenylhex-5-enylcarbamate (9e). The
general procedure 3 described above was followed when 8 (147
mg, 0.5 mmol) was treated with but-1-enylmagnesium bromide
(4-bromo-1-butene, 0.20 mL, 2.0 mmol; Mg, 49 mg, 2.0 mmol)
in dry THF (2 mL) at 0 °C with stirring at rt for 1 h to afford 9e as
a white solid (124 mg, 86% yield). Mp 59-61 °C; Rf 0.53 (ethyl
acetate-petroleum ether, 1:4); [R]25D þ250.0 (c 0.6, CH2Cl2); IR
νmax (KBr, cm-1) 3299, 3064, 2980, 2935, 1721, 1699, 1680,
1542, 1495, 1455, 1409, 1392, 1367, 1323, 1279, 1253, 1171, 1091,
1075, 1054, 1030, 1009, 997, 969, 915, 887, 779, 749, 705, 619,
582; 1H NMR (CDCl3, 500 MHz) δ 1.39 (s, 9H), 2.11-2.29 (m,
2H), 2.39-2.50 (m, 2H), 4.87-4.91 (m, 2H), 5.26 (d, J = 6.0 Hz,
tert-Butyl (1S,2R)-2-Hydroxy-1-phenylhex-5-enylcarbamate
(10e). The general procedure 4 described above was followed
when 9e (289 mg, 1.0 mmol) was treated with NaBH4 (76 mg, 2.0
mmol) in dry MeOH (10 mL) at -20 °C for 1 h to afford 10e as a
white solid (291 mg, quantitative yield). Mp 100-102 °C; Rf 0.46
(ethyl acetate-petroleum ether, 1:3); IR νmax (KBr, cm-1) 3370,
3065, 3042, 3005, 2971, 2942, 1680, 1643, 1531, 1457, 1415, 1392,
1368, 1346, 1299, 1252, 1171, 1108, 1080, 1037, 1011, 964, 933,
905, 888, 873, 843, 780, 755, 737, 704, 668, 633, 594, 517, 461; 1H
NMR (CDCl3, 500 MHz) δ 1.19-1.26 (m, 1H), 1.39 (s, 9H),
1.48-1.54 (m, 1H), 2.07-2.12 (m, 1H), 2.18-2.23 (m, 1H), 3.87
(br s, 1H), 4.60 (br s, 1H), 4.92-5.00 (m, 2H), 5.40 (br s, 1H),
5.72-5.77 (m, 1H), 7.24-7.34 (m, 5H); 13C NMR (125 MHz,
CDCl3) δ 28.4, 30.2, 33.2, 59.2, 73.9, 79.8, 115.3, 126.6, 127.8,
128.6, 138.1, 155.5.
N-((1S,2R)-2-Hydroxy-1-phenylbutyl)-4-methylbenzenesulfo-
namide (11a).20a The general procedure 5 described above was
followed when 10a (265 mg, 1.0 mmol) was treated with TFA
(1.0 mL) in dry CH2Cl2 (5 mL) at 0 °C and stirred for 1 h at rt. To
the reaction mixture was added Et3N (2.2 mL) and TsCl (229
mg, 1.2 mmol) at 0 °C with stirring for 2 h at the same
temperature to afford 11a as a white solid (275 mg, 86% yield).
Mp 126-128 °C; Rf 0.18 (ethyl acetate-petroleum ether, 1:3);
[R]25D þ45.0 (c 2.05, CH2Cl2); IR νmax (KBr, cm-1) 3490, 3293,
3067, 2965, 2936, 2904, 2877, 1598, 1497, 1454, 1418, 1396, 1378,
1363, 1319, 1306, 1264, 1158, 1134, 1088, 1066, 1039, 1020, 997,
965, 913, 808, 762, 704, 664, 623, 596, 566, 544; 1H NMR
(CDCl3, 500 MHz) δ 0.89 (t, J = 7.6 Hz, 3H), 1.04-1.13 (m,
1H), 1.30-1.41 (m, 1H), 2.32 (s, 3H), 3.76-3.79 (m, 1H), 4.32
(dd, J = 8.3, 3.8 Hz, 1H), 5.52 (d, J = 8.3 Hz, 1H), 7.01-7.18
(m, 7H), 7.49 (d, J = 8.3 Hz, 2H); 13C NMR (125 MHz, CDCl3)
δ 10.3, 21.5, 26.7, 61.6, 76.0, 127.1, 127.7, 127.9, 128.3, 129.3,
136.4, 137.4, 143.1.
1H), 5.59-5.67 (m, 1H), 5.89 (br s, 1H), 7.25-7.37 (m, 5H); 13
NMR (125 MHz, CDCl3) δ 27.5, 28.1, 28.3, 38.7, 64.2, 79.9,
115.5, 127.9, 128.5, 129.2, 136.4, 136.9, 154.9, 205.2.
C
tert-Butyl (1S,2R)-2-Hydroxy-1-phenylbutylcarbamate (10a).
The general procedure 4 described above was followed when 9a
(263 mg, 1.0 mmol) was treated with NaBH4 (76 mg, 2.0 mmol)
in dry MeOH (10 mL) at -20 °C for 1 h to afford 10a as a white
solid (265 mg, quantitative yield). Mp 128-130 °C; Rf 0.36
(ethyl acetate-petroleum ether, 1:3); [R]25 þ24.0 (c 0.55,
D
CH2Cl2); IR νmax (KBr, cm-1) 3377, 3009, 2971, 2931, 1681,
1528, 1460, 1389, 1368, 1321, 1297, 1255, 1228, 1173, 1110, 1082,
1043, 1019, 967, 883, 856, 840, 754, 706, 647, 615, 596, 518; 1H
NMR (CDCl3, 400 MHz) δ 0.89 (t, J = 7.6 Hz, 3H), 0.95-1.42
(m, 2H), 1.35 (s, 9H), 3.71-3.73 (m, 1H), 4.59 (br s, 1H), 5.38 (br
s, 1H), 7.19-7.29 (m, 5H); 13C NMR (125 MHz, CDCl3) δ 10.3,
27.0, 28.3, 58.7, 75.8, 79.6, 126.5, 127.7, 128.4, 138.4, 155.4.
tert-Butyl (1S,2R)-2-Hydroxy-1-phenylpentylcarbamate (10b).
The general procedure 4 described above was followed when 9b
(277mg, 1.0 mmol) wastreated with NaBH4 (76 mg, 2.0mmol) in
dry MeOH (10 mL) at -20 °C for 1 h to afford 10b as a white
solid (279 mg, quantitative yield). Mp 143-145 °C; Rf 0.43 (ethyl
acetate-petroleum ether, 1:3); [R]25D þ35.0 (c 1.7, CH2Cl2); IR
ν
max (KBr, cm-1) 3370, 3047, 3006, 2968, 2917, 2872, 1680, 1531,
1459, 1391, 1369, 1296, 1254, 1172, 1136, 1109, 1045, 1015, 955,
914, 881, 842, 780, 755, 705, 665, 631, 596, 518, 461; 1H NMR
(CDCl3, 500 MHz) δ 0.86 (t, J = 7.25 Hz, 3H), 1.08-1.17 (m,
1H), 1.23-1.53 (m, 3H), 1.38 (s, 9H), 3.86-3.88 (m, 1H), 4.63 (br
s, 1H), 5.45 (br s, 1H), 7.22-7.36 (m, 5H); 13C NMR (125 MHz,
CDCl3) δ 13.9, 19.0, 28.3, 36.1, 58.9, 74.0, 79.7, 126.5, 127.6,
128.4, 138.4, 155.4.
N-((1S,2R)-2-Hydroxy-1-phenylpentyl)-4-methylbenzenesul-
fonamide (11b). The general procedure 5 described above was
followed when 10b (279 mg, 1.0 mmol) was treated with TFA
(1.0 mL) in dry CH2Cl2 (5 mL) at 0 °C and stirred for 1 h at rt. To
the reaction mixture was added Et3N (2.2 mL) and TsCl (229
mg, 1.2 mmol) at 0 °C with stirring for 2 h to afford 11a as a
white solid (293 mg, 88% yield). Mp 113-115 °C; Rf 0.23 (ethyl
acetate-petroleum ether, 1:3); [R]25D þ47.0 (c 2.3, CH2Cl2); IR
νmax (KBr, cm-1) 3505, 3328, 3033, 2954, 2869, 1599, 1496,
1457, 1413, 1378, 1342, 1319, 1289, 1259, 1195, 1158, 1120, 1090,
1053, 1033, 1020, 935, 917, 893, 809, 761, 704, 691, 663, 600, 572,
546, 523; 1H NMR (CDCl3, 400 MHz) δ 0.81 (t, J = 7.1 Hz, 3H),
1.02-1.03 (m, 1H), 1.22-1.29 (m, 2H), 1.37-1.40 (m, 1H), 2.31
(s, 3H), 3.83-3.88 (m, 1H), 4.28 (dd, J = 8.1, 3.7 Hz, 1H), 5.48
(d, J = 8.1 Hz, 1H), 7.00-7.16 (m, 7H), 7.48 (d, J = 8.3 Hz, 2H);
13C NMR (125 MHz, CDCl3) δ 13.8, 18.9, 21.4, 35.7, 61.8, 74.1,
126.9, 127.6, 127.9, 128.2, 129.2, 136.3, 137.4, 143.0.
tert-Butyl (1S,2R)-2-Hydroxy-1-phenylhexylcarbamate (10c).
The general procedure 4 described above was followed when 9c
(291 mg, 1.0 mmol) was treated with NaBH4 (76 mg, 2.0 mmol)
in dry MeOH (10 mL) at -20 °C for 1 h to afford 10c as a white
solid (293 mg, quantitative yield). Mp 106-108 °C; Rf 0.47
(ethyl acetate-petroleum ether, 1:3); [R]25 þ15.0 (c 1.1,
D
CH2Cl2); IR νmax (KBr, cm-1) 3372, 3040, 3005, 2967, 2936,
2873, 1681, 1529, 1460, 1391, 1368, 1344, 1296, 1252, 1172, 1078,
1044, 1017, 1002, 884, 843, 779, 756, 703, 664, 631, 597, 518; 1H
NMR (CDCl3, 500 MHz) δ 0.85 (t, J = 7.2 Hz, 3H), 1.09-1.53
(m, 6H), 1.40 (s, 9H), 3.84-3.86 (m, 1H), 4.64 (br s, 1H), 5.46 (br
s, 1H), 7.25-7.35 (m, 5H); 13C NMR (125 MHz, CDCl3) δ 13.9,
22.5, 27.9, 28.3, 33.7, 58.9, 74.3, 79.7, 126.5, 127.6, 128.4, 138.4,
155.4.
N-((1S,2R)-2-Hydroxy-1-phenylhexyl)-4-methylbenzenesul-
fonamide (11c). The general procedure 5 described above was
followed when 10c (293 mg, 1.0 mmol) was treated with TFA
(1.0 mL) in dry CH2Cl2 (5 mL) at 0 °C and stirred for 1 h at rt.
To the reaction mixture was added Et3N (2.2 mL) and TsCl
(229 mg, 1.2 mmol) at 0 °C with stirring for 2 h to afford 11c as
a white solid (313 mg, 90% yield). Mp 133-135 °C; Rf 0.27
tert-Butyl (1S,2R)-2-Hydroxy-1-phenylpent-4-enylcarbamate
(10d).20b The general procedure 4 described above was followed
when 9d (275 mg, 1.0 mmol) was treated with NaBH4 (76 mg, 2.0
mmol) in dry MeOH (10 mL) at -20 °C for 1 h to afford 10d as a
white solid (277 mg, quantitative yield). Rf 0.39 (ethyl aceta-
te-petroleum ether, 1:3); IR νmax (KBr, cm-1) 3381, 3070, 3006,
2975, 2926, 2855, 1688, 1526, 1457, 1390, 1367, 1294, 1252, 1172,
(ethyl acetate-petroleum ether, 1:3); [R]25 þ43.0 (c 2.15,
D
CH2Cl2); IR νmax (KBr, cm-1) 3499, 3324, 3090, 3065, 3035,
2939, 2922, 2858, 1599, 1495, 1458, 1411, 1379, 1352, 1318, 1288,
1266, 1253, 1195, 1156, 1087, 1055, 1020, 912, 842, 809, 760,
J. Org. Chem. Vol. 75, No. 1, 2010 147