Asymmetric Synthesis and Properties of Sulfinimines
J . Org. Chem., Vol. 62, No. 8, 1997 2563
for C14H12NOS: C, 64.28; H, 4.59; N, 5.35. Found: C, 64.62;
H, 4.89; N, 5.29.
2957, 1621, 1492, 1465, 1142, 1097, 1074, 1017, 810 cm-1; 1H
NMR (CDCl3) δ 0.95 (q, 3H, J ) 3.6, 6.7 Hz), 2.09-1.98 (m,
3H), 2.4 (s, 1H), 7.27 (d, 1H, J ) 8.3 Hz), 7.53 (d, 1H, J ) 8.2
Hz), 8.20 (t, J ) 5.4 Hz, 1H); 13C NMR (CDCl3) δ 166.8, 141.6,
(S)-(+)-N-(p-Nitr oben zylid en e)-p-tolu en esu lfin a m id e
(10f): yield 95%; purification, flash chromatography 45%
EtOAc/hexane; mp 157-158.5 °C; [R]20 +19.8° (c 1.1 CHCl3);
129.8, 124.5, 44.6, 26.2, 22.5, 21.4. Anal. Calcd for C12H17-
D
IR (KBr) 1588, 806 cm-1; 1H NMR (CDCl3) δ 2.41 (s, 3 H), 7.34
(d, 2 H, J ) 8.1 Hz), 7.64 (d, 2 H, J ) 8.2 Hz), 8.01 (d, 2 H, J
) 8.8 Hz), 8.30 (d, 2 H, J ) 8.8 Hz), 8.82 (s, 1 H); 13C NMR
(CDCl3) δ 158.2, 149.7, 142.0, 140.6, 138.7, 130.1, 129.9, 124.6,
123.9, 21.5. Anal. Calcd for C14H12N2O3S: C, 58.32; H, 4.20;
N, 9.71. Found: C, 58.19; H, 4.48; N, 9.87.
NOS: C, 64.57; H, 7.62; N, 6.27. Found: C, 64.33; H, 7.45;
N, 5.92.
(S)-(+)-N-Isob u t ylid en e-p -t olu en esu lfin a m id e (10o):
yield 60%; oil; flash chromatography (20% ether in pentane);
1
[R]20 +387.5° (c 2.1, CHCl3); IR (neat) 1732, 1619, cm-1; H
D
NMR (CDCl3) δ 0.98 (d, 3H, J ) 2.9 Hz), 1.01 (d, 3H, J )
2.8Hz), 2.45 (s, 3H), 2.46-2.58 (m, 1H), 7.13 (d, 2H, J ) 8.1
Hz), 7.40 (d, 2H, J ) 8.2 Hz), 7.98 (d, 1H, J ) 4.6 Hz); 13C
NMR (CDCl3) δ 170.9, 141.8, 141.3, 129.5, 124.4, 34.6, 21.4,
18.7. Anal. Calcd for C11H15NOS: C, 63.12; H, 7.22. Found:
C, 62.96; H, 7.23.
(R)-(-)-N-(3-P yr id in em et h ylid en e)-p -t olu en esu lfin a -
m id e (10j): yield 70%; isolated by flash chromatography using
70% EtOAc/hexane and crystallized from n-hexane:EtOAc; mp
77-78 °C (lit.7c mp 77-78 °C); [R]20D -149.8° (c 1.17, CHCl3).7c
(S)-(+)-N-(3-P yr id in em et h ylid en e)-p -t olu en esu lfin a -
m id e (10j): [R]20 147.0° (c 1.34, CHCl3).
D
(S)-(+)-N-(2,2-Dim eth ylp r op ylid en e)-p-tolu en esu lfin a -
m id e (10p ). The reaction mixture was stirred overnight at
rt, quenched at -78 °C, and worked up as usual: yield 68%;
(S )-(+)-N -(2-F u r y lm e t h y lid e n e )-p -t o lu e n e s u lfin a -
m id e (10k ): yield 68%; purification, flash chromatography
20% EtOAc/hexane; mp 65 °C; [R]20 +78.3 (c 0.65 CHCl3); IR
crystallization from n-pentane; mp 73-75 °C; [R]20 +371.5°
D
D
(KBr) 1700, 1652, 1216, 770, 669 cm-1; 1H NMR (CDCl3) δ 2.32
(s, 3 H), 6.49-6.47 (m, 1H), 6.96 (d, 2 H, J ) 3.6 Hz), 7.24 (d,
2 H, J ) 8.1 Hz), 7.56 (d, 2 H, J ) 8.1 Hz), 8.51 (s,1H); 13C
NMR (CDCl3) δ 15.0.3, 147.5, 146.9, 141.7, 141.42, 129.74,
124.5, 119.2, 112.4, 21.2. Anal. Calcd for C12H11NO2S: C,
61.78; H,4.75; N, 6.00. Found: C, 61.72; H, 4.71; N, 5.89.
(S)-(+)-N-(2-Th ien ylm et h ylid en e)-p -t olu en esu lfin a -
m id e (10l): yield 72%; purification, flash chromatography 20%
EtOAc/hexane; mp 82 °C; [R]20D -96.4 (c 0.69 CHCl3); IR (KBr)
1582, 819, 717 cm-1; 1H NMR (CDCl3) δ 2.34 (s, 3 H), 7.07 (t,
1H, J ) 4.2 Hz), 7.25 (d, 2 H, J ) 9.0 Hz), 7.50-7.58 (m, 4 H),
8.80 (s, 1 H); 13C NMR (CDCl3) δ 153.4, 141.6, 139.8, 134.2,
(c 1.94, CHCl3);5a IR (KBr): 1612 cm-1; 1H NMR (CDCl3) δ 1.14
(s, 9H), 2.40 (s, 3H), 7.30 (d, 2H, J ) 8.2 Hz), 7.55 (d, 2H, J )
8.2 Hz), 8.08 (s, 1H); 13C NMR (CDCl3) δ 173.4, 142.2, 141.5,
129.7, 124.7, 37.7, 26.5, 21.4. Anal. Calcd for C12H17NOS: C,
64.54; H, 7.67; N, 6.20. Found: C, 64.41; H, 7.60; N, 5.88.
(S )-(+)-N -(2-P h e n y le t h y lid e n e )-p -t o lu e n e s u lfin a -
m id e (10q). To isolate this sulfinimine is was necessary to
wash the chromatographic solvents with concd NH4OH. The
solvents were then used to precondition the silica gel column:
isolated yield 38%; thick gum; flash chromatography (20%
ether in n-pentane, saturated with ammonia); [R]20 +256.1°
D
(c 1.0, CHCl3); IR (neat) 3389, 3027, 2916, 1613, 1494, 1453,
132.6, 129.7, 128.0, 124.7, 21.3. Anal. Calcd for C12H11
-
1093, 623 cm-1 1H NMR (CDCl3) δ 2.38 (s, 3H), 3.68-3.83
;
NO2S2: C, 57.83; H, 4.42; N, 5.62. Found: C, 57.71; H, 4.41;
N, 5.48.
(m, 2H), 7.15-7.29 (m, 7H), 7.52 (d, J ) 8.1Hz, 2H), 8.24 (t, J
) 5.4 Hz, 1H); 13C NMR (CDCl3) δ 165.7, 142.5, 130.5, 129.9,
129.6, 129.5, 128.8, 128.7, 127.9, 125.2, 43.0.
(S )-(+)-N -(C r o t o n y li d e n e )-p -t o lu e n e s u lfi n a m i d e
(10c): yield 70%; purification, flash chromatography 20%
(S)-(+)-N-(S)-p-Tolu en esu lfin yl)-â-styr en ylen am in e (16):
yield 40%; thick gum; flash chromatography (20% ether in
n-pentane); [R]20D +121.3 (c 1.0, CHCl3); IR (KBr) 3362-3100,
EtOAc/hexane; [R]20 +617.0° (c 1.7, CHCl3); mp 39-40 °C;
D
IR (KBr) 1645, 1572, 967, 813 cm-1; H NMR (CDCl3) δ 1.96
1
(dd, 3H, J ) 6.6, 1.2 Hz), 2.39 (s, 3H), 6.35-6.66 (m, 2H), 7.30
(d, 2H, J ) 7.9 Hz), 7.56 (d, 2H, J ) 8.2 Hz),, 8.34 (d, 1H, J )
9.0 Hz); 13C NMR (CDCl3) δ 161.6, 147.1, 141.8, 141.5, 130.0,
129.7, 124.5, 21.5, 19.0. Anal. Calcd. for C11H13NOS: C,
63.74; H,6.32; N, 6.76. Found: C, 63.62; H, 6.52; N, 6.66.
(S )-(+)-N -(C in n a m y lid e n e )-p -t o lu e n e s u lfin a m id e
(10d ): yield 80%; crystallized from ether; [R]20D +337° (c 1.49,
CHCl3); mp 114-115 °C; IR (KBr) 1627, 1581, 994, 960, 811
1
3028, 811 cm-1; H NMR (CDCl3) δ 2.44 (s, 3H), 6.02 (d, J )
13.8 Hz, 1H), 6.14 (d, J ) 10.8 Hz, 1H), 6.75 (dd, J ) 11.1,
14.0 Hz, 1H), 7.18-7.37 (m, 7H), 7.65 (d, J ) 8.1 Hz, 2H).
(S )-(+)-N -(2,2,2-T r ip h e n y le t h y lid e n e )-p -t o lu e n e -
su lfin a m id e (10r ): yield 50%; flash chromatography (10%
EtOAc/pentane); mp 114-115 °C; [R]20 +126.0° (c 0.63,
D
CHCl3); IR (KBr) 1609, 807 cm-1; H NMR (CDCl3) δ 2.40 (s,
1
3 H), 7.00-7.02 (m, 6 H), 7.25-7.28 (m, 11 H), 7.48 (d, 2 H, J
) 8.1 Hz), 8.98 (s, 1 H); 13C NMR (CDCl3) δ 169.3, 143.2, 142.1,
130.9, 130.3, 128.7, 128.5, 127.7, 125.5, 64.4, 22.0. Anal. Calcd
for C27H23NOS: C, 79.18; H, 5.66; N, 3.42. Found: C, 79.55;
H, 5.95; N, 3.31.
1
cm-1; H NMR (CDCl3) δ 2.39 (s, 3H), 7.05 (dd, 1H, J ) 15.8,
9.1 Hz), 7.21-7.52 (m, 8H), 7.59 (d, 2H, J ) 8.1 Hz), 8.52 (d,
2H, J ) 9.1Hz); 13CNMR (CDCl3) δ 161.4, 146.7, 141.7, 134.7,
130.2, 129.8, 128.8, 127.8, 125.4, 124.4, 21.6. Anal. Calcd for
C16H15NOS: C, 71.34; H, 5.61; N, 5.20. Found: C, 71.45; H,
5.76; N, 5.22.
Ack n ow led gm en t. This work was supported by
grants from the National Institutes of Health and the
National Science Foundation.
(S )-(+)-N -(P r o p e n y lid e n e )-p -t o lu e n e s u lfin a m id e
(10m ): yield 71%; oil; flash chromatography (20% ether in
pentane); [R]20 +729° (c 2.2, CHCl3); IR (KBr) 1624, 948, 810
D
cm-1
;
1H NMR (CDCl3) δ 2.39 (s, 3H), 5.89 (s, 1H), 6.04 (d,
1H, J ) 6.3 Hz), 6.66 (m, 1H), 7.33 (d, 2H, J ) 8.1 Hz), 7.57
(d, 2H, J ) 8.3 Hz), 8.37 (d, 1H, J ) 9.3 Hz); 13CNMR (CDCl3)
δ 161.9, 141.8, 141.4, 134.5, 132.1, 129.8, 124.6, 21.4. Anal.
Calcd for C10H11NOS: C, 62.14; H, 5.73; N, 7.24. Found: C,
62.40; H, 6.00; N, 7.60.
Su p p or t in g In for m a t ion Ava ila b le: 1H and 13C NMR
spectra of 10q, 12c, 14, 16, and a mixture of 14 and 15 (7
pages). This material is contained in libraries on microfiche,
immediately follows this article in the microfilm version of the
journal, and can be ordered from the ACS; see any current
masthead page for ordering information.
(S )-(+)-N -(3-Me t h y lb u t y lid e n e )-p -t o lu e n e s u lfin a -
m id e (10n ): yield 68% (thick gum); flash chromatography
(20% ether in pentane); [R]20 +317° (c 1.4, CHCl3); IR (neat)
J O970077E
D