9460 J . Org. Chem., Vol. 63, No. 25, 1998
Alonso and Andersson
in dry DMF (3 mL) was added to a suspension of K2CO3 (65
mg, 0.48 mmol) and thiophenol (20 µL, 0.16 mmol) in DMF (3
mL). The reaction mixture was stirred for 12 h and extracted
with ether and water. The organic phase was washed with
water (3 × 10 mL), dried (MgSO4), and evaporated to afford
the crude ring opening product. Purification by flash chroma-
tography (silica gel, pentane/EtOAc, 4/1) afforded the pure
yellow product in a 92% yield.
N-[(2S)-3-P h en yl-1-th iop h en oxyp r op yl]-4-m eth ylben -
zen esu lfon a m id e: Rf 0.53 (pentane/EtOAc, 3/1); [R]25D -69.2
(c 0.5, CHCl3); IR (neat, cm-1) 3252, 1531, 1347, and 1160; 1H
NMR δ 2.71 (1 H, dd, J ) 14.0, 8.0 Hz), 2.95 (1 H, dd, J )
14.0, 6.8 Hz), 3.08 (1 H, dd, J ) 14.0, 5.6 Hz), 3.22 (1 H, dd, J
) 14.0, 4.8 Hz), 3.48 (1 H, m), 4.95 (1 H, br d, J ) 7.2 Hz),
6.92 (2 H, d, J ) 6.4 Hz), 7.58, 8.02 (2 H each, 2d, J ) 8.8 Hz),
7.10-7.30 (8 H, m). 13C NMR δ 38.8, 40.1, 55.2, 124.2, 127.0,
127.2, 128.2, 129.0, 129.38, 129.42, 129.8, 134.8, 136.6, 145.3,
and 149.9; MS (EI) m/z (rel intensity) 429 (M+ + 1, 26), 428
(M+, 45), 305 (17), 227 (32), 136 (11), 135 (100), 124 (37), 120
(13), 119 (91), 118 (33), 117 (25), 91 (18), and 89 (11). Anal.
Calcd for C21H20N2O4S2: C, 58.86; H, 4.70; N, 6.54. Found: C,
58.73; H, 4.79; N, 6.72.
Gen er a l P r oced u r e for Dissolved Meta l Red u ction s.
A suspension in dry THF (15 mL) of the corresponding metal
(Li, Na or Ca) (10 or 2 equiv) was dissolved in liquid ammonia
at -78 °C under an argon atmosphere in a three-necked flask
equipped with a dry acetone-cooled Dewar condenser. To this
blue solution was added the aziridine (0.5 mmol) solved in dry
THF (3 mL), and the reaction was kept at -78 °C with stirring
for 45 min (4 h for the reactions with Ca). Brine (10 mL) was
then added cautiously to the reaction flask, followed by the
addition of CH2Cl2 (10 mL). The ammonia in the solution was
then allowed to evaporate, and the reaction mixture was
extracted with two more portions of CH2Cl2. The combined
organic phases were dried over MgSO4, filtered, and concen-
trated. The residue was then purified by flash chromatography
(deactivated silica gel, ether/acetone) to provide the corre-
sponding products.
(2R)-P h en yla zir id in e (9):34 Rf 0.35 (EtOAc); tR ) 9.34 min;
D
1
[R]20 -31.5 (c 1.4, CHCl3); IR (film, cm-1) 3303; H NMR δ
1.50 (1 H, br s), 1.81 (1 H, d, J ) 3.2 Hz), 2.21 (1 H, d, J ) 6.0
Hz), 3.02 (1 H, m), and 7.15-7.40 (5 H, m); 13C NMR δ 29.2,
32.1, 125.6, 126.7, 128.2, and 140.7; MS (EI) m/z (rel intensity)
119 (M+, 15), 118 (100), 117 (25), 91 (36), 89 (17), 65 (12), 63
(13), and 51 (13).
N-(2-P h en yleth yl)tolu en e-4-su lfon a m id e (10):35 All the
physical and spectroscopic data were in complete agreement
with the reported ones.
Cycloh exyl (3S)-Met h yl-1-a zir id in -(2S)-ca r b oxyla t e
(11): Rf 0.26 (pentane/EtOAc, 1/1); tR 13.05 min; [R]24 +15.3
D
(c 1, CHCl3); IR (film, cm-1) 3419, 1722, and 1202; 1H NMR δ
1.20-1.60 (10 H, m with d at 1.27, J ) 6.0 Hz), 1.65-1.95 (2
H each, 2m), 2.26 (1 H, m), 2.58 (1 Η, br d, J ) 6.0 Hz), and
4.82 (1 H, m); 13C NMR δ 12.9, 23.6, 23.7, 25.2, 31.5, 31.7,
33.5, 35.1, 73.8, and 170.2; MS (EI) m/z (rel intensity) 184 (M+
+ 1, <1), 101 (38), 83 (76), 56 (24), 55 (100), and 54 (10). Anal.
Calcd for C17H25NO4S: C, 60.15; H, 7.42; N, 4.13. Found: C,
60.10; H, 7.30; N, 4.29.
Cycloh exyl (3S)-(p -Tolu en esu lfon a m id o)b u t a n oa t e
(12): Rf 0.64 (pentane/EtOAc, 3/1); IR (film, cm-1) 3600-3050,
1
1725, 1332, 1161, and 1091; H NMR δ 1.14 (3 Η, d, J ) 6.8
Hz), 1.20-1.40, 1.64-1.84 (10 H, 2m), 2.37 (2 H, d, J ) 5.6
Hz), 2.42 (3 H, s), 3.68 (1 H, m), 4.71 (1 H, m), 5.19 (1 H, br d,
J ) 8.0 Hz), 7.29 and 7.75 (2 H each, 2d, J ) 8.0 Hz); 13C
NMR δ 21.0, 21.5, 23.7, 25.4, 31.47, 31.55, 40.8, 46.7, 73.3,
127.0, 129.7, 138.1, 143.3, and 170.6; MS (EI) m/z (rel
intensity) 341 (M+ + 2, 35), 340 (M+ + 1, 84), 322 (12), 274
(49), 258 (12), 242 (16), 240 (17), 220 (21), 198 (79), 184 (53),
155 (39), 102 (100), and 91 (29).
Gen er a l P r oced u r e for Meta l/Na p h th a len e Red u c-
tion s. To a cooled (-78 °C) green suspension of the corre-
sponding metal (Na or Li, 1.44 mmol) and naphthalene (208
mg, 1.62 mmol) in dry THF (4 mL) was added the correspond-
ing aziridine (0.36 mmol) under argon, and the mixture was
stirred for 45 min at the same temperature. Then, the reaction
was hydrolyzed with brine (10 mL) and extracted with CH2-
Cl2 (3 × 10 mL). The combined organic layers were dried over
anhydrous MgSO4 and evaporated. The resulting residue was
purified by flash chromatography (deactivated silica gel, ether/
acetone) to yield the corresponding pure products.
Gen er a l P r oced u r e for Rea ction s w ith Li a n d a Ca ta -
lytic Am ou n t of DTBB. To a cooled (-78 °C) green suspen-
sion of Li powder (15 mg, 2.16 mmol) and DTBB (6 mg, 0.011
mmol) in dry THF (4 mL) was slowly added (ca. 1 h) the
corresponding aziridine (0.22 mmol) under argon, and the
mixture was stirred for 60 min at the same temperature. Then,
the reaction was hydrolyzed with brine (10 mL) and extracted
with CH2Cl2 (3 × 10 mL). The combined organic layers were
dried over anhydrous MgSO4 and evaporated. The resulting
residue was purified by flash chromatography (deactivated
silica gel, ether/acetone) to yield the corresponding pure
products.
(2S)-Ben zyla zir id in e (4):32 Rf 0.35 (acetone); tR ) 10.25
min; [R]24D -7.7 (c 1.82, CHCl3); IR (film, cm-1) 3254; 1H NMR
δ 0.80 (1 H, m), 1.45 (1 H, d, J ) 3.6 Hz), 1.82 (1 H, br d, J )
5.6 Hz), 2.16-2.25 (1 H, m), 2.65 (1 H, dd, J ) 14.8, 6.4 Hz),
2.80 (1 H, dd, J ) 14.8, 6.0 Hz), and 7.20-7.35 (5 H, m); 13C
NMR δ 24.8, 30.9, 40.0, 126.3, 128.3, 128.7, and 139.0; MS
(EI) m/z (rel intensity) 133 (M+, 25), 132 (69), 118 (17), 117
(17), 104 (39), 103 (40), 92 (18), 91 (100), 89 (28), 78 (39), 77
(49), 65 (26), 63 (26), 62 (20), 56 (28), 51 (51), and 50 (39).
(S)-Ben zyleth ylen ed ia m in e (5): Rf 0.22 (pentane/EtOAc,
1
3/1); tR ) 11.40 min; IR (film, cm-1) 3385; H NMR δ 1.80 (1
H, dd, J ) 6.0, 2.8 Hz), 1.99 (1 H, dd, J ) 8.4, 2.4 Hz), 2.31 (1
H, m), 2.60 (1 H, dd, J ) 14.8, 6.4 Hz), 2.74 (1 H, dd, J ) 14.8,
7.2 Hz), 6.01 (1 H, br s), 7.22-7.35 (5 H, m); 13C NMR δ 37.1,
37.5, 43.4, 126.4, 128.5, 128.7, and 138.4; MS (EI) m/z (rel
intensity) 132 (M+ - 15, 40), 130 (27), 118 (18), 117 (100), 105
(37), 104 (81), 103 (38), 92 (11), 91 (71), 79 (17), 78 (40), 77
(16), and 65 (17).
Gen er a l P r oced u r e for Sm I2 Red u ction s. To a 0.1 M
24
solution of SmI2 (2.5 equiv for aziridine 3, 6 equiv for
aziridines 1a , 1b, and 2) in dry THF was added a THF solution
of the corresponding aziridines at 0 °C. The reaction mixture
was then stirred at room temperature (aziridine 3) or refluxed
with 6 equiv of DMPU as cosolvent (for aziridines 1a , 1b, and
2) for 15 h, quenched with brine (15 mL), and extracted with
CH2Cl2 (3 × 15 mL). The organic layer was dried over
anhydrous MgSO4 and evaporated. The resulting residue was
purified by flash chromatography (deactivated silica gel) to
yield pure products 13-15.
Gen er a l P r oced u r e for Ma gn esiu m Red u ction s. To a
suspension of Mg (40 mg, 1.6 mmol) in anhydrous MeOH (3
mL) was added a solution of the corresponding aziridine (0.3
mmol) in anhydrous MeOH (2 mL). The resulting suspension
was stirred or sonicated (methods A and B in Table 2) for 30
min until comsumption of the starting material (reaction
minitored by TLC) was complete. The reaction was then
diluted with brine (5 mL) and extracted with CH2Cl2 (3 × 5
mL). The organic layer was dried over MgSO4 and evaporated.
The resulting residue was purified by flash chromatography
(deactivated silica gel) to yield pure products 4 and 8-12.
N-(3-P h en ylp r op yl)-tolu en e-4-su lfon a m id e (8):33 All the
physical and spectroscopic data were in complete agreement
with the reported ones.
N-[3-P h en yl-(2E)-p r op en yl]-4-m et h ylb en zen esu lfon -
a m id e (13):36 mp 109-110 °C (EtOAc); IR (KBr, cm-1) 3386,
1
1330, and 1160; H NMR δ 2.42 (3 H, s), 3.78 (2 Η, dd, J )
6.2, 5.0 Hz), 4.67 (1 H, br s), 6.04 (1 H, dt, J ) 16.0, 6.2 Hz),
6.46 (1 H, d, J ) 16.0 Hz), 7.20-7.32 (7 H, m), and 7.78 (2 H,
d, J ) 8.0 Hz); 13C NMR δ 21.5, 45.6, 124.1, 126.4, 127.2, 128.0,
(32) Kelly, J . W.; Eskew, N. L.; Evans, S. A., J r. J . Org. Chem. 1986,
51, 95.
(33) William, R.; Proctor, G. R. J . Chem. Soc., Perkin Trans. 1 1981,
(34) Perlman, M. E.; Bardos, Th. J . J . Org. Chem. 1988, 53, 1761.
(35) Yang, R.-Y.; Dai, L.-X. Synthesis 1993, 481.
2443.
(36) Oppolzer, W.; Stammen, B. Tetrahedron 1997, 53, 3577.