Catalytic Asymmetric Sulfimidation
J . Org. Chem., Vol. 62, No. 19, 1997 6517
EIMS (m/z) 369 (M+), 214 (M+ - Ts). Anal. Calcd for C20H19
-
2.36 (s, 3H, CH3), 2.37 (s, 3H, CH3), 3.98 (d, J ) 6.4 Hz, 2H,
CH2), 5.14 (dd, J ) 17.0, 1.4 Hz, 1H, CHdCHH), 5.15 (dd, J )
10.0, 1.4 Hz, 1H, CHdCHH), 5.76 (ddt, J ) 17.0, 10.0, 6.4 Hz,
1H, CHdCH2), 7.24 (d, J ) 8.4 Hz, 2H), 7.73 (d, J ) 8.4 Hz,
2H); 13C NMR δ 21.6, 23.6, 56.4, 119.2, 127.8, 129.5, 133.2,
136.1, 143.8; EIMS (m/z) 257 (M+), 102 (M+ - Ts). Anal.
Calcd for C11H15NO2S2: C, 51.34; H, 5.87; N, 5.44. Found: C,
51.27; H, 5.87; N, 5.37.
NO2S2: C, 65.01; H, 5.18; N, 3.79. Found: C, 64.96; H, 5.27;
N, 3.73.
S-Ben zyl-S-(4-m eth oxyp h en yl)-N-(p-tolylsu lfon yl)su l-
filim in e (2e): 25 colorless needles; 70% yield; eluent, hexane/
Et2O ) 1/4; mp 127.5-128.0 °C; 1H NMR δ 2.31 (s, 3H, CH3),
3.81 (s, 3H, CH3), 4.10 (d, J ) 12.5 Hz, 1H), 4.33 (d, J ) 12.5
Hz, 1H), 6.86-7.62 (m, 13H).
N-Allyl-N-(a llylth io)-p-tolu en esu lfon a m id e (5b): color-
less needles; 82% yield; eluent, hexane/Et2O ) 7/1; mp 74.5-
75.5 °C (lit.15a mp 72 °C); 1H NMR δ 2.43 (s, 3H, CH3), 3.53 (d,
J ) 7.4 Hz, 2H, CH2), 4.07 (d, J ) 6.3 Hz, 2H, CH2), 5.16 (dd,
J ) 10.5, 1.4 Hz, 1H, CHdCHH), 5.18 (dd, J ) 17.2, 1.4 Hz,
1H, CHdCHH), 5.19 (dd, J ) 9.8, 1.4 Hz, 1H, CHdCHH), 5.21
(dd, J ) 17.0, 1.4 Hz, 1H, CHdCHH), 5.74 (ddt, J ) 17.0, 9.8,
7.4 Hz, 1H, CHdCH2), 5.85 (ddt, J ) 17.2, 10.5, 6.3 Hz, 1H,
CHdCH2), 7.30 (d, J ) 8.5 Hz, 2H), 7.80 (d, J ) 8.5 Hz, 2H).
N-(1-P h en yla llyl)-N-(p h en ylt h io)-p -t olu en esu lfon a -
m id e (5c): colorless needles; 75% yield; eluent, hexane/Et2O
S-Ben zyl-S-(2-n it r op h en yl)-N-(p -t olylsu lfon yl)su lfil-
im in e (2f): colorless needles; 53% yield; eluent, CH2Cl2/MeOH
) 70/1; mp 194.0-195.0 °C; IR (KBr) 1533 (NO2), 1347 (NO2),
1280, 1137, 1088, 1021, 1005 cm-1 1H NMR δ 2.33 (s, 3H,
;
CH3), 4.17 (d, J ) 11.9 Hz, 1H), 4.49 (d, J ) 11.9 Hz, 1H),
6.98-8.62 (m, 13H); 13C NMR δ 21.3, 60.0, 125.7, 125.9, 128.3,
128.8, 129.0, 129.2, 130.8, 132.8, 134.0, 136.0, 140.4, 141.4,
145.3. Anal. Calcd for C20H18N2O4S2: C, 57.96; H, 4.38; N,
6.76. Found: C, 57.68; H, 4.44; N, 6.55.
S-(4-Nitr op h en ylm eth yl)-S-p h en yl-N-(p-tolylsu lfon yl)-
su lfilim in e (2g): colorless needles; 72% yield; eluent, CH2Cl2;
mp 197.0-198.0 °C; IR (KBr) 1522 (NO2), 1344 (NO2), 1292,
1278, 1020, 1003, 988, 749 cm-1; 1H NMR δ 2.31 (s, 3H, CH3),
4.28 (s, 2H, CH2), 7.04-8.10 (m, 13H); 13C NMR δ 21.2, 58.6,
123.5, 126.0, 126.3, 129.1, 130.0, 131.8, 132.9, 133.5, 134.5,
140.9, 141.9, 148.2. Anal. Calcd for C20H18N2O4S2: C, 57.96;
H, 4.38; N, 6.76. Found: C, 57.16; H, 4.47; N, 6.44.
S-Ben zyl-S-(1-n a p h th a len yl)-N-(p-tolylsu lfon yl)su lfil-
im in e (2h ): colorless needles; 54% yield; eluent, hexane/Et2O
) 1/4; mp 153.5-154.5 °C; IR (KBr) 1281, 1149, 1140, 1086,
1021, 991, 967 cm-1; 1H NMR δ 2.42(s, 3H, CH3), 4.07 (d, J )
12.9 Hz, 1H), 4.28 (d, J ) 12.9 Hz, 1H), 6.88-7.95 (m, 16H);
13C NMR δ 21.3, 59.2, 121.3, 125.7, 126.1, 127.0, 127.7, 128.0,
128.6, 128.9, 129.1, 130.6, 132.7, 133.5, 141.3; EIMS (m/z) 264
(M+ - Ts). Anal. Calcd for C24H21NO2S2: C, 68.71; H, 5.04;
N, 3.34. Found: C, 68.45; H, 5.28; N, 3.34.
1
) 7/1; mp 82.5-83.5 °C (lit.15c mp 88 °C); H NMR δ 2.31 (s,
3H, CH3), 5.03 (dd, J ) 18.0, 1.1 Hz, 1H, CHdCHH), 5.16 (dd,
J ) 11.0, 1.1 Hz, 1H, CHdCHH), 5.99 (br. s, 1H), 6.05 (ddd, J
) 18.0, 11.0, 6.5 Hz, 1H, CHdCH2), 7.12-7.25 (m, 12H), 7.68
(br, 2H).
N-(1-P h en yla llyl)-N-(2-n itr op h en ylth io)-p-tolu en esu l-
fon a m id e (5d ): colorless needles; 35% yield; eluent, hexane/
Et2O ) 7/1; mp 162-163 °C; IR (KBr) 1593, 1513 (NO2), 1344,
1
1335 (NO2), 1310, 1161, 990, 885, 735, 705 cm-1; H NMR δ
2.33 (s, 3H, CH3), 4.91 (d, J ) 16.5 Hz, 1H), 5.10 (d, J ) 10.2
Hz, 1H), 5.92-6.07 (m, 2H), 6.99-8.31 (m, 13H); 13C NMR δ
21.6, 67.1, 119.1, 124.6, 125.5, 126.0, 127.7, 128.0, 128.2, 129.0,
129.3, 129.7, 134.2, 134.8, 136.9, 144.4; EIMS (m/z) 440 (M+);
HRMS calcd for C22H20N2O4S2 440.0864, found 440.0852.
Anal. Calcd for C22H20N2O4S2: C, 59.98; H, 4.58; N, 6.36.
Found: C, 59.13; H, 4.55; N, 6.10.
S,S-Dip h en yl-N-(p-tolylsu lfon yl)su lfilim in e (2i): color-
less needles; 79% yield; eluent, hexane/Et2O ) 1/6; mp 109.0-
109.5 °C (lit.26 mp 111-112 °C); 1H NMR δ 2.43 (s, 3H, CH3),
7.29-7.83 (m, 14H).
N-(1-P h en yla llyl)-N-(1-n a p h t h a len ylt h io)-p -t olu en e-
su lfon a m id e (5e): clear oil; 80% yield; eluent, hexane/Et2O
) 7/1; IR (neat) 1164, 1089, 933, 908, 812, 792, 769, 733, 702,
670, 594 cm-1; 1H NMR δ 2.35 (s, 3H, CH3), 5.04 (dd, J ) 16.2,
1.4 Hz, 1H, CHdCHH), 5.11 (dd, J ) 10.2, 1.4 Hz, 1H,
CHdCHH), 6.05 (d, J ) 6.7 Hz, 1H, CH), 6.11 (ddd, J ) 16.2,
10.2, 6.7 Hz, 1H, CHdCH2), 7.03-7.89 (m, 16H); 13C NMR δ
21.5, 60.0, 116.9, 125.3, 126.8, 127.9, 128.7, 129.5, 136.7, 137.2,
143.9; EIMS (m/z) 260 (M+ - CH2dCH2C10H7S). Anal. Calcd
for C26H23NO2S2: C, 70.08; H, 5.20; N, 3.14. Found: C,
70.04: H, 5.28; N, 3.08.
S-P h en yl-S-(2-p h en ylet h yl)-N-(p -t olylsu lfon yl)su lfil-
im in e (2j): colorless needles; 50% yield; eluent, hexane/Et2O
1
) 1/4; mp 137.0-138.0 °C (lit.21 mp 137-138 °C); H NMR δ
2.34 (s, 3H, CH3), 2.85-2.95 (m, 2H), 3.07-3.17 (m, 1H), 3.27-
3.35 (m, 1H), 7.01-7.79 (m, 14H).
S-E t h yl-S-m et h yl-N-(p -t olylsu lfon yl)su lfilim in e (2k ):
colorless needles; 50% yield; eluent, Et2O/MeOH ) 4/1; mp
1
131.5-132.0 °C (lit.27 mp 133 °C); H NMR δ 1.25 (t, J ) 7.4
N-(1-Met h yla llyl)-N-(1-p h en ylt h io)-p -t olu en esu lfon a -
m id e (5f): colorless needles; 44% yield; eluent, hexane/Et2O
) 7/1; mp 63.5-64.5 °C; IR (KBr) 1350, 1166, 894, 819, 746,
Hz, 3H, CH3), 2.39 (s, 3H, CH3), 2.59 (s, 3H, CH3), 2.88 (q, J
) 7.4 Hz, 2H, CH2), 7.25 (d, J ) 7.4 Hz, 2H), 7.78 (d, J ) 7.4
Hz, 2H).
1
670, 569, 550 cm-1; H NMR δ 1.26 (d, 3H, CH3), 2.42 (s, 3H,
S-[(E t h oxyca r b on yl)m et h yl]-S-m et h yl-N-(p -t olylsu l-
fon yl)su lfilim in e (2l): colorless needles; 53% yield; eluent,
CH2Cl2/MeOH ) 40/1; mp 73.5-74.5 °C; IR (KBr) 1748 (CdO),
1282, 1134, 1086, 1000, 965, 749 cm-1; 1H NMR δ 1.28 (t, J )
7.1 Hz, 3H, CH3), 2.40 (s, 3H, CH3), 2.86 (s, 3H, CH3), 3.94 (s,
2H, CH2), 4.01-4.24 (m, 2H), 7.25 (d, J ) 8.2 Hz, 2H), 7.78
(d, J ) 8.2 Hz, 2H); 13C NMR δ 13.9, 21.4, 34.5, 53.7, 62.9,
126.3, 129.3, 141.0, 142.1; EIMS (m/z) 303 (M+); HRMS calcd
for C12H17NO4S2 303.0599; found 303.0589. Anal. Calcd for
C12H17NO4S2: C, 47.51; H, 5.65; N, 4.62. Found: C, 47.42; H,
5.51; N, 4.62.
CH3), 4.90-5.00 (m, 3H), 5.60 (br s, 1H), 7.17-7.84 (m, 9H);
13C NMR δ 21.5, 60.0, 116.9, 125.2, 126.2, 126.8, 127.9, 128.7,
129.5, 136.7, 137.2, 138.9, 143.9; EIMS (m/z) 333 (M+). Anal.
Calcd for C17H19NO2S2: C, 61.23; H, 5.74; N, 4.20. Found: C,
61.28; H, 5.81; N, 4.20.
N-(1-Met h yla llyl)-N-(1-n a p h t h a len ylt h io)-p -t olu en e-
su lfon a m id e (5g): clear oil; 55% yield; eluent, hexane/Et2O
) 7/1; IR (neat) 1354, 1165, 1089, 909, 769, 733, 669 cm-1; 1H
NMR δ 1.18 (d, J ) 6.6 Hz, 3H, CH3), 2.38 (s, 3H, CH3), 4.92-
5.08 (m, 3H), 5.64 (ddd, J ) 17.0, 10.5, 6.6 Hz, 1H, CHdCH2),
7.23-7.98 (m, 11H); 13C NMR δ 18.4, 21.4, 60.2, 117.0, 122.4,
123.1, 125.80, 125.85, 125.96, 126.52, 127.9, 128.5, 129.5,
133.3, 135.3, 136.6, 136.9, 144.0; EIMS (m/z) 383 (M+); HRMS
calcd for C21H21NO2S2 383.1014, found 383.1011.
Typ ica l P r oced u r e for Asym m etr ic Im id a tion of Su l-
fid e. To a solution of CuOTf (2.60 mg, 0.010 mmol, 0.050
equiv) and 4,4′-disubstituted bis(oxazoline) 6a (4.11 mg, 0.012
mmol, 0.060 equiv) in 1.0 mL of toluene were added first
TsNdIPh (75.0 mg, 0.20 mmol, 1.0 equiv) and then the sulfide
(0.20 mmol, 1.0 equiv), and the resulting mixture was stirred
under nitrogen at 25 °C for 48 h as shown in Tables 5 and 6.
The mixture was then added with brine and extracted with
dichloromethane. The extract was dried over anhydrous
MgSO4, and the evaporation of the solvent left a crude product.
Purification by silica gel column chromatography gave the
corresponding enantiopure sulfimide. Enantiomeric excesses
S-Ben zyl-S-m eth yl-N-(p-tolylsu lfon yl)su lfilim in e (2m ):
1
colorless needles; 70% yield; eluent, EtOAc; H NMR δ 2.33
(s, 3H, CH3), 2.50 (s, 3H, CH3), 4.21 (AB, J ) 12.5, 38.9 Hz,
2H, CH2), 7.10 (d, J ) 8.1 Hz, 2H), 7.26 (m, 5H, Ph), 7.60 (d,
J ) 8.1 Hz, 2H). Anal. Calcd for C15H17NO2S2: C, 58.60; H,
5.57; N, 4.56. Found: C, 58.62; H, 5.55; N, 4.45.
N-Allyl-N-(m eth ylth io)-p-tolu en esu lfon a m id e (5a ): col-
orless needles; 78% yield; eluent, hexane/Et2O ) 1/1; mp 68.5-
69.5 °C; IR (KBr) 2991, 2919, 2852, 1435, 1345, 1333, 1160,
1089, 1067, 935, 826, 810, 661, 593, 546, 537 cm-1; 1H NMR δ
(25) Kim, K. S.; J ung, I. B.; Kim, Y. H.; Oae, S. Tetrahedron Lett.
1989, 30, 1087.
(26) Furukawa, N.; Yoshimasa, T.; Omata, T.; Oae, S. Chem. Ind.
(London) 1974, 702.
(27) Mann, F. G.; Pope, W. J . J . Chem. Soc. 1922, 121, 1052.