8242 J . Org. Chem., Vol. 66, No. 24, 2001
Notes
3
3
SiCH3), 0.96 (d, J HH ) 6.8 Hz, 3 H, CCHCH3), 0.97 (d, J HH
)
4c (major diastereomer): mp 175-176 °C; [RD]20 ) -44.4;
3
1
6.8 Hz, 3 H, CCHCH3), 1.38 (d, J HH ) 6.8 Hz, 6 H, NCHCH3),
1.39 (d, 3J HH ) 6.8 Hz, 6 H, NCHCH3), 1.47 (d, 3J HH ) 6.8 Hz, 6
H, NCHCH3), 1.50 (d, 3J HH ) 6.8 Hz, 6 H, NCHCH3), 1.58 (ddd,
3J HH ) 5.2 Hz, 2J HH ) 8.4 Hz, 3J PH ) 13.6 Hz, 1 H, CHring), 2.12
(ddd, 3J HH ) 8.0 Hz, 2J HH ) 8.4 Hz, 3J PH ) 16.8 Hz, 1 H, CHring),
31P{1H} NMR (C6D6): δ 95.7; H NMR (CDCl3): δ 0.24 (s, 9 H,
3
3
SiCH3), 1.20 (d, J HH ) 6.8 Hz, 6 H, NCHCH3), 1.22 (d, J HH
)
3
6.8 Hz, 6 H, NCHCH3), 1.24 (d, J HH ) 6.8 Hz, 6 H, NCHCH3),
1.33 (d, J HH ) 6.8 Hz, 6 H, NCHCH3), 1.50 (ddd, J HH ) 5.0
3
2
3
3
2
Hz, J HH ) 7.8 Hz, J PH ) 21.6 Hz, 1 H, CHring), 1.76 (ddd, J HH
) 5.0 Hz, 3J HH ) 3.7 Hz, 3J PH ) 23.4 Hz, 1 H, CHring), 2.49 (ddd,
3J HH ) 3.7 Hz, 3J HH ) 7.8 Hz, 3J PH ) 12.2 Hz, 1 H, CHring), 3.64
2
3
3
2.27 (ddd, J HH ) 5.2 Hz, J HH ) 8.0 Hz, J PH ) 22.8 Hz, 1 H,
3
3
CHring), 2.52 (sept d, J HH ) 6.8 Hz, J HH ) 3.6 Hz, 1 H,
3
3
3
3
CCHCH3), 4,02 (sept d, J HH ) 6.8 Hz, J PH ) 15.6 Hz, 2 H,
(sept d, J HH ) 6.8 Hz, J PH ) 19.2 Hz, 2 H, NCHCH3), 4.50 (m,
2 H, NCHCH3), the protons of sultam were omitted for clarity;
2
3
NCHCH3), 4.20 (dd, J HH ) 0.8 Hz, J HH ) 8.0 Hz, 1 H, OCH2),
3
3
1
4,27 (sept d, J HH ) 6.8 Hz, J PH ) 12.4 Hz, 2 H, NCHCH3),
4.34 (t, 3J HH ) 2J HH ) 8.0 Hz, 1 H, OCH2), 4.38 (ddd, 3J HH ) 8.0
Hz, 3J HH ) 1.2 Hz, 3J HH ) 3.6 Hz, 1 H, OCH2CH); 13C{1H} NMR
(CDCl3): _ 1.4 (s, SiCH3), 15.1 (s, CCHCH3), 18.3 (s, CCHCH3),
20.0 (d, 1J PC ) 95.0 Hz, PC), 21.7 (s, CH2ring), 23.5 (s, NCHCH3),
13C{1H} NMR (CDCl3): δ 1.8 (s, SiCH3), 17.8 (d, J PC ) 91.0 Hz,
PC), 20.5 (s, CCH3), 21.7 (s, CCH3), 22.0 (s, CH2ring), 23.8 (s,
CHCH2CH2), 24.1 (s, NCHCH3), 24.5 (s, NCHCH3), 25.6 (d, 3J PC
3
) 6.0 Hz, NCHCH3), 25.7 (d, J PC ) 4.6 Hz, NCHCH3), 27.0 (s,
CCH2CH2C), 32.9 (d, 2J PC ) 7.3 Hz, CHring), 33.8 (s, CCH2CH2C),
3
2
24.1 (s, NCHCH3), 25.2 (d, J PC ) 6.0 Hz, NCHCH3), 25.4 (d,
37.4 [s, CH2SO2], 45.5 [s, CCH2CHN], 47.8 (d, J PC ) 4.8 Hz,
3J PC ) 5.0 Hz, NCHCH3), 29.0 (s, CCHCH3), 32.4 (d, J PC ) 6.0
CH3CHN), 48.1 [s, (CH3)2CC(CH2)2], 48.2 (d, J PC ) 6.7 Hz,
2
2
2
2
Hz, CHring), 47.4 (d, J PC ) 5.0 Hz, CHN), 47.5 (d, J PC ) 7.0
Hz, CH3CHN), 60.9 (s, OCH2CHN), 63.9 (s, OCH2), 154.6 (s,
O(N)CdO), 169.6 (s, C(N)CdO). Anal. Calcd for C25H50N3O3-
PSSi: C, 56.46; H, 9.48; N, 7.90. Found: C, 56.52; H, 9.53; N,
7.88.
CH3CHN), 48.5 [s, (CH3)2CC(CH2)2], 54.0 (s, CCH2SO2), 66.7 (s,
CHN), 169.0 (d, 3J PC ) 8.0 Hz, CdO). Anal. Calcd for C29H56N3O3-
PS2Si: C, 56.37; H, 9.13; N, 6.80. Found: C, 56.42; H, 9.15; N,
6.75.
5-(R,R): [RD]20 ) 10; 5-(S,S): [RD]20 ) -12; 31P{1H} NMR
4′b (minor diastereomer): mp 150-152 °C; [RD]20 ) -65; 31P-
(CDCl3): δ 76.4; H NMR (CDCl3): δ 1.21 (d, J HH ) 6.5 Hz, 6
1
3
{1H} NMR (C6D6): δ 91.5; 1H NMR (CDCl3): δ 0.32 (s, 9 H,
H, NCHCH3), 1.23 (d, J HH ) 6.5 Hz, 6 H, NCHCH3), 1.32 (d,
3
3
3
SiCH3), 0.94 (d, J HH ) 6.4 Hz, 3 H, CCHCH3), 0.96 (d, J HH
)
3J HH ) 6.5 Hz, 12 H, NCHCH3), 1.44 (m, 1 H, CHring), 1.62 (m,
3
6.4 Hz, 3 H, CCHCH3), 1.38 (d, J HH ) 6.8 Hz, 6 H, NCHCH3),
1.39 (d, 3J HH ) 6.8 Hz, 6 H, NCHCH3), 1.46 (d, 3J HH ) 6.8 Hz, 6
H, NCHCH3), 1.51 (d, 3J HH ) 6.8 Hz, 6 H, NCHCH3), 1.54 (ddd,
3J HH ) 4.8 Hz, 2J HH ) 8.0 Hz, 3J PH ) 12.4 Hz, 1 H, CHring), 2.05
(ddd, 3J HH ) 4.8 Hz, 3J HH ) 7.2 Hz, 3J PH ) 22.8 Hz, 1 H, CHring),
2.53 (m, 2 H, CCHCH3 and CHring), 4,10 (m, 2 H, NCHCH3),
1 H, CHring), 1.73 (m, 1 H, CHring), 2.25 (m, 1 H, CHring), 3.73
3
3
(sept d, J HH ) 6.5 Hz, J PH ) 11.9 Hz, 4 H, NCHCH3), 9.3 (s
broad, 1 H, OH); 13C{1H} NMR (CDCl3): δ 22.8 (d, J PC ) 22.5
Hz, CHring), 22.9, 23.1, 23.7, 24.0 (s, NCHCH3), 29.5 (s, CH2ring),
46.5 (d, J PC ) 5.9 Hz, CH3CHN), 46.6 (d, J PC ) 5.0 Hz, CH3CHN),
179.1 (d, J PC ) 3.0 Hz, CdO); MS (EI) 348 (M+).
3
3
3
4,17 (sept d, J HH ) 6.8 Hz, J PH ) 12.0 Hz, 2 H, NCHCH3),
3
3
Ack n ow led gm en t. Thanks are due to the CNRS for
financial support of this work, to the French Embassy
in Tokyo and the French-Polish Associate European
Laboratory for grants (to T.K. and J .K.).
4.21 (dd, J HH ) 2.4 Hz, J HH ) 8.8 Hz, 1 H, OCH2), 4.32 (t,
3J HH
)
2J HH ) 8.4 Hz, 1 H, OCH2), 4.45 (ddd, J HH ) 8.4 Hz,
3
3
3J HH ) 2.4 Hz, J HH ) 3.6 Hz, 1 H, OCH2CH); 13C{1H} NMR
(CDCl3): δ 1.7 (s, SiCH3), 14.4 (s, CCHCH3), 18.1 (s, CCHCH3),
18.8 (s, CH2ring), 23.7 (s, NCHCH3), 24.1 (d, 1J PC ) 86.0 Hz, PC),
3
24.2 (s, NCHCH3), 25.1 (d, J PC ) 5.0 Hz, NCHCH3), 25.3 (d,
Su p p or tin g In for m a tion Ava ila ble: X-ray crystallo-
graphic studies for compounds 4a , 4b, 4′b, and 4c. This
material is available free of charge via the Internet at
http://pubs.acs.org.
3J PC ) 6.0 Hz, NCHCH3), 28.4 (s, CCHCH3), 33.5 (d, J PC ) 5.0
2
Hz, CHring), 47.6 (d, 2J PC ) 5.0 Hz, CH3CHN), 60.2 (s, OCH2CHN),
3
63.5 (s, OCH2), 154.3 (s, O(N)CdO), 169.5 (d, J PC ) 10.0 Hz,
C(N)CdO). Anal. Calcd for C25H50N3O3PSSi: C, 56.46; H, 9.48;
N, 7.90. Found: C, 56.50; H, 9.51; N, 7.92.
J O010586N