The Journal of Organic Chemistry
Note
2
0
1
Yield 258 mg, 79%. [α] D2 0 +6.0 (c = 1, CHCl ). 1H NMR (500
8
(
4−87 °C. Yield 91 mg, 25%. [α] +18.0 (c = 1, CHCl ). H NMR
D
3
3
500 MHz, CDCl ) δ 7.93 (d, J = 7.5 Hz, 1H), 7.67 (t, J = 7.5 Hz,
MHz, CDCl ) δ 7.94 (d, J = 7.9 Hz, 1H), 7.71 (t, J = 7.2 Hz, 1H), 7.60
3
3
1H), 7.55 (t, J = 7.8 Hz, 1H), 5.01 (d, J = 9.8 Hz, 1H), 4.68 (d, J = 9.0
(t, J = 7.9 Hz, 1H), 4.54 (m, 1H), 4.23 (m, 1H), 3.68 (m, 1H), 3.57
Hz, 1H), 4.12 (m, 1H), 3.97 (d, J = 9.3 Hz, 1H), 1.36 (s, 9H), 1.20 (d,
(dd, J = 6.1, 1.0 Hz, 1H), 1.44 (s, 9H), 1.23 (d, J = 6.9 Hz, 3H) ppm.
J = 6.8 Hz, 2H) ppm. 13C NMR (125 MHz, CDCl ) δ 155.4, 135.3,
13
C NMR (125 MHz, CDCl ) δ 154.9, 137.1, 134.5, 129.4, 128.8, 80.2,
3
3
1
34.6, 129.6, 129.2, 79.6, 73.5, 73.4, 47.2, 28.2, 18.4 ppm. HRMS
67.6, 59.5, 46.4, 28.2, 17.0 ppm. HRMS (ESI) calcd for
+
+
(
ESI) calcd for C H ClNNaO S ([M + Na] ) 386.0805, found
C H NNaO S ([M + Na] ) 350.1038, found 350.1039. IR (NaCl)
1
5
22
5
15 21
5
3
1
6
86.0800. IR (NaCl) ν 3390, 3020, 2980, 2930, 1711, 1498, 1449,
ν 3019, 2980, 1748, 1733, 1699, 1684, 1498, 1473, 1457, 1329, 1157,
−1
393, 1368, 1345, 1322, 1311, 1152, 1100, 1081, 1060, 1018, 998, 822,
1087, 686, 418 cm .
−1
99, 686, 578, 553, 543, 456, 432, 418 cm .
Spectroscopic Data for tert-Butyl ((S)-1-((2R,3S)-3-
Spectroscopic Data for tert-Butyl ((2S,3S,4S)-4-Chloro-3-hydroxy-
(Phenylsulfonyl)oxiran-2-yl)ethyl)carbamate (12). Colorless oil.
Yield 229 mg, 70%. [α]2 −2.0 (c = 1, CHCl ). H NMR (500
0
1
4
-(phenylsulfonyl)butan-2-yl)carbamate (2). White solid, mp 87−91
D
3
C. Yield 73 mg, 20%. [α]2 −10.0 (c = 1, CHCl ). H NMR (500
0
D
1
°
MHz, CDCl ) δ 7.93 (d, J = 7.3 Hz, 1H), 7.73 (t, J = 7.5 Hz, 1H), 7.61
3
3
MHz, CDCl ) δ 7.99 (d, J = 7.6 Hz, 1H), 7.76 (d, J = 7.3 Hz, 1H),
(t, J = 7.8 Hz, 1H), 4.55 (s, 1H), 4.15 (m, 1H), 3.87 (m, 1H), 3.70 (m,
3
1H), 1.43 (s, 9H), 1.28 (d, J = 6.9 Hz, 3H) ppm. 13C NMR (125 MHz,
7.64 (t, J = 7.7 Hz, 1H), 5.04 (s, 1H), 4.52 (d, J = 9.6 Hz, 1H), 4.24 (d,
J = 9.5 Hz, 1H), 4.16 (m, 1H), 4.05 (s, 1H), 1.45 (s, 9H), 1.14 (d, J =
CDCl ) δ 154.6, 136.9, 134.5, 129.5, 128.8, 80.1, 67.5, 59.9, 44.4, 28.3,
3
.6 Hz, 2H) ppm. 1 C NMR (125 MHz, CDCl ) δ 155.1, 135.0, 134.6,
3
+
6
1
18.2 ppm. HRMS (ESI) calcd for C H NNaO S ([M + Na] )
3
15 21
5
30.2, 129.3, 79.6, 73.3, 71.4, 47.6, 28.2, 13.0 ppm. HRMS (ESI) calcd
350.1038, found 350.1034. IR (NaCl) ν 3020, 2981, 1710, 1499, 1456,
+
−1
for C H ClNNaO S ([M + Na] ) 386.0805, found 386.0805. IR
1449, 1369, 1329, 1311, 1233, 1017, 583 cm .
15
22
5
(
1
5
NaCl) ν 3444, 3019, 2980, 2360, 2342, 1707, 1500, 1449, 1393, 1368,
Spectroscopic Data for tert-Butyl ((S)-1-((2S,3R)-3-
348, 1312, 1220, 1153, 1136, 1099, 1058, 1024, 997, 818, 686, 577,
(Phenylsulfonyl)oxiran-2-yl)ethyl)carbamate (13). Colorless oil.
−1
20
1
58, 532, 487, 461, 430, 418 cm .
Yield 209 mg, 64%. [α]
D
−4.0 (c = 1, CHCl ). H NMR (500
3
Spectroscopic Data for tert-Butyl ((2S,3R,4S)-4-Chloro-3-hy-
MHz, CDCl ) δ 7.93 (d, J = 7.3 Hz, 1H), 7.71 (t, J = 7.5 Hz, 1H), 7.60
3
droxy-4-(phenylsulfonyl)butan-2-yl)carbamate (3). White solid, mp
8
(
(t, J = 7.8 Hz, 1H), 4.55 (s, 1H), 4.25 (m, 1H), 3.68 (m, 1H), 3.57
(dd, J = 6.1, 1.5 Hz, 1H), 1.44 (s, 9H), 1.23 (d, J = 6.9 Hz, 3H) ppm.
2
0
1
5−90 °C. Yield 65 mg, 18%. [α] −14.0 (c = 1, CHCl ). H NMR
D
3
13
300 MHz, CDCl ) δ 7.96 (d, J = 8.0 Hz, 1H), 7.68 (t, J = 7.0 Hz,
C NMR (125 MHz, CDCl ) δ 154.9, 137.1, 134.4, 129.4, 128.8, 80.2,
3
3
1
4
H), 7.57 (t, J = 7.6 Hz, 1H), 4.85 (s, 1H), 4.79 (d, J = 8.4 Hz, 1H),
.51 (s, 1H), 3.92 (m, 1H), 3.34 (m, 1H), 1.40 (s, 9H), 1.25 (d, J = 6.8
67.5, 59.5, 46.4, 28.3, 17.0 ppm. HRMS (ESI) calcd for
+
C H NNaO S ([M + Na] ) 350.1038, found 350.1044. IR (NaCl)
15
21
5
13
Hz, 2H) ppm. C NMR (75 MHz, CDCl ) δ 156.8, 136.0, 135.2,
1
for C H ClNNaO S ([M + Na] ) 386.0805, found 386.0811. IR
ν 3019, 1714, 1497, 1456, 1448, 1369, 1330, 1312, 1157, 1087, 687,
3
−1
30.7, 129.5, 80.7, 76.9, 71.3, 50.8, 28.9, 18.5 ppm. HRMS (ESI) calcd
584 cm .
General Experimental Procedure for the Preparation of
+
15
22
5
(
NaCl) ν 3444, 3019, 2980, 2934, 1703, 1504, 1449, 1393, 1368, 1345,
Chloroketone 14 from Chlorohydrin 1. To an ice-bath-cold
solution of chlorohydrin 1 (363.5 mg, 1 mmol) in DCM (5 mL) was
added slowly Dess−Martin periodinane (424.1 mg, 1 mmol) in one
portion. The reaction mixture was stirred for 2 h, and then the reaction
was quenched with sodium thiosulfate (10%)/sodium carbonate
saturated aqueous solution (1:1) (25 mL). The mixture was stirred for
30 min and then extracted with DCM (3 × 15 mL), and the organic
layers were washed with brine, dried (Na SO ), and concentrated. The
1
5
322, 1311, 1156, 1101, 1083, 1055, 1026, 998, 686, 576, 559, 540,
03, 472, 429, 418 cm .
−1
Spectroscopic Data for tert-Butyl ((2S,3S,4R)-4-Chloro-3-hy-
droxy-4-(phenylsulfonyl)butan-2-yl)carbamate (4). White solid, mp
8
2
0
1
5−89 °C. Yield 44 mg, 12%. [α] +20.0 (c = 1, CHCl ). H NMR
D
3
(
500 MHz, CDCl ) δ 7.97 (d, J = 7.3 Hz, 1H), 7.72 (t, J = 7.5 Hz,
3
1
H), 7.60 (t, J = 7.8 Hz, 1H), 4.95 (s, 1H), 4.58 (d, J = 7.7 Hz, 1H),
.45 (d, J = 7.6 Hz, 1H), 3.84 (s, 1H), 3.16 (s, 1H), 1.42 (s, 9H), 1.30
2
4
4
crude material was purified by chromatography (silica gel, hexanes/
ethyl acetate (7:3)) to afford the desired compound (yield 321 mg,
89%).
General Experimental Procedure for the Preparation of
Chloroketones from Esters. To a stirred solution of chloromethyl
phenyl sulfone (3 mmol) in THF (10 mL) at −78 °C was added
slowly n-BuLi (1.6 M in hexanes, 3 mmol), and the mixture was stirred
for 30 min. The amino ester (1 mmol) in THF (5 mL) was added, and
the resulting mixture was gradually warmed to rt and stirred overnight.
(
d, J = 6.7 Hz, 2H) ppm. 13C NMR (125 MHz, CDCl ) δ 155.6, 135.5,
3
134.8, 130.0, 129.2, 80.1, 74.7, 71.5, 49.0, 28.3, 17.5 ppm. HRMS
+
(
ESI) calcd for C H ClNNaO S ([M + Na] ) 386.0805, found
1
5
22
5
3
1
86.0804. IR (NaCl) ν 3378, 3019, 2980, 1707, 1504, 1449, 1393,
368, 1324, 1312, 1154, 1083, 1049, 1028, 686, 587, 576, 540 cm .
−1
General Experimental Procedure for the Preparation of
Epoxysulfones from Chlorohydrins. To an ice-bath-cold solution
of chlorohydrin (1 mmol) in DCM/tert-butanol (1:1) (3 mL) was
added slowly sodium tert-butoxide (0.95 mmol) in one portion. The
mixture was stirred for 30 min, and then the reaction was quenched
with ammonium chloride saturated aqueous solution (25 mL). The
resulting mixture was extracted with DCM (3 × 15 mL), and then the
organic layers were washed with 1 M hydrochloric acid (15 mL),
sodium bicarbonate saturated aqueous solution (15 mL), and brine,
dried (Na SO ), and concentrated. The crude material was purified by
The reaction was quenched with NH Cl saturated solution (25 mL).
4
The resulting mixture was extracted with ethyl ether (3 × 15 mL), and
then the organic layers were washed with brine, dried (Na SO ), and
2
4
concentrated. The crude material was purified by chromatography
(silica gel, hexanes/ethyl acetate (7:3)) to afford the desired
compound (yield 217 mg, 60%).
2
4
Spectroscopic Data for tert-Butyl ((2S)-4-Chloro-3-oxo-4-
chromatography (silica gel, hexanes/ethyl acetate (7:3)) to afford the
desired compound.
(phenylsulfonyl)butan-2-yl)carbamate (14). White solid, mp 103−
106 °C. [α]2
0
−8.0 (c = 1, CHCl ). H NMR (300 MHz, CDCl ) δ
3 3
1
D
Spectroscopic Data for tert-Butyl ((S)-1-((2R,3R)-3-
7.91 (d, J = 7.7 Hz, 4H), 7.74 (t, J = 7.5 Hz, 2H), 7.60 (t, J = 7.5 Hz,
(
Phenylsulfonyl)oxiran-2-yl)ethyl)carbamate (10). Colorless oil.
4H), 5.87 (s, 1H), 5.75 (s, 1H), 5.29 (s, 1H), 4.99 (s, 1H), 4.71 (s,
Yield 275 mg, 84%. [α]D +2.0 (c = 1, CHCl3). 1H NMR (500
20
13
2H), 1.48 (s, 9H), 1.43 (s, 15H) ppm. C NMR (75 MHz, CDCl ) δ
3
MHz, CDCl ) δ 7.93 (d, J = 8.3 Hz, 1H), 7.71 (t, J = 6.9 Hz, 1H), 7.60
196.7, 155.0, 135.3, 135.2, 134.3, 130.6, 130.4, 129.1, 81.0, 80.7, 73.3,
3
(
t, J = 7.6 Hz, 1H), 4.37 (br s, 1H), 4.17−4.08 (m, 1H), 4.00 (t, J = 1.4
71.9, 55.5, 54.7, 28.3, 28.2, 17.2, 16.1 ppm. HRMS (ESI) calcd for
+
Hz, 1H), 3.69 (d, J = 1.3 Hz, 1H), 1.42 (s, 9H), 1.26 (d, J = 7.0 Hz,
3
1
C H NNaO S ([M + Na] ) 350.1038, found 350.1032. IR (NaCl) ν
3
6
C H ClNNaO S ([M + Na] ) 384.0648, found 384.0642. IR (NaCl)
15
20
5
H) ppm. 13C NMR (125 MHz, CDCl ) δ 154.8, 136.0, 134.5, 129.4,
ν 3019, 2981, 2930, 1771, 1540, 1498, 1449, 1394, 1369, 1331, 1313,
3
−1
28.8, 80.1, 66.3, 59.9, 44.3, 28.3, 18.4 ppm. HRMS (ESI) calcd for
1158, 1082, 1072, 1032, 1007, 686, 570, 553, 533, 525, 514, 418 cm .
General Experimental Procedure for the Preparation of
Oxazolidinones. To an ice-bath-cold solution of chlorohydrin (1
mmol) in DCM (3 mL) was added slowly trifluoroacetic acid/DCM
(1:1) (3 mL). The mixture was stirred for 30 min and directly
concentrated. DCM (5 mL) and then phosphate buffer (pH 9) were
+
15
21
5
020, 2981, 1712, 1498, 1449, 1393, 1368, 1327, 1265, 1083, 1058,
−1
86, 580, 555 cm .
Spectroscopic Data for tert-Butyl ((S)-1-((2S,3S)-3-
(
Phenylsulfonyl)oxiran-2-yl)ethyl)carbamate (11). Colorless oil.
D
J. Org. Chem. XXXX, XXX, XXX−XXX