H. Tye et al. / Tetrahedron Letters 43 (2002) 155–158
157
amine (1.0 mL, 7.0 mmol) was added and the mixture
3.6. (S,S)-N,N%-Dimethyl-1,2-diphenylethylenediamine
cooled to 0°C. Phenyl phosphinic dichloride (0.51 mL,
3.51 mmol) was added slowly dropwise. After 30 min
the mixture was allowed to warm to room temperature
and stirred overnight. The reaction was quenched by
the addition of water and the separated organics were
dried over sodium sulfate, filtered and the solvent evap-
orated to give 6 as a pale yellow solid (696 mg, 84%);
mp 186–188°C; [h]2D0=+4.3 (c 0.51, methanol); (found:
C, 60.6; H, 7.4; N, 11.6. C12H17N2OP requires: C,
61.02; H, 7.20; N, 11.86%); wmax 3215, 1312, 1201, 1183,
1108, 1075, 951, 897 and 744 cm−1; lH (400 MHz,
CDCl3) 7.92–7.87 (2H, m), 7.51–7.40 (3H, m), 3.30 (1H,
m), 3.08–3.02 (1H, m), 2.96 (1H, d, J=12.2), 2.86 (1H,
d, J=5.9), 1.95 (1H, m), 1.85 (1H, m), 1.81 (2H, m),
1.56–1.35 (4H, m); lC (68 MHz, CD3OD) 26.2 (t), 26.8
(dt, JPC=4.4), 34.8 (t), 36.2 (t), 57.1 (dd, JPC=5.5), 59.1
(dd, JPC=18), 129.8, 129.9, 130.0, 130.1, 132.6, 132.8,
132.9, 133.6; lP (162 MHz, CDCl3) 25.8; m/z 236 (M+,
100%), 194 (7), 101 (77), 86 (47); (found [M]+,
236.1037. C12H17N2OP requires m/z, 236.1078).
53f
(S3,S4)-1-Phenyl-(3,4-diphenyl)diazaphospholidine
1-
oxide 7 was prepared from 3 in the same way as
reported for 6 in quantitative yield; lH (270 MHz,
CDCl3) 8.11–8.04 (2H, m), 7.54 (3H, s), 7.29 (7H, s),
7.20 (3H, s), 4.69 (1H, d, J=8.8), 4.53 (1H, d, J=8.8),
3.30 (1H, d, 15.4), 3.24 (1H, d, J=9.0). Compound 7
was then converted into (S3,S4)-1-phenyl-N,N%-
dimethyl-(3,4-diphenyl)diazaphospholidine 1-oxide
9
using the method described for 8 in 96% yield; lH (270
MHz, CDCl3) 8.03–7.95 (2H, m), 7.64–7.53 (3H, m),
7.33–7.10 (10H, m), 4.25 (1H, d, J=8.8), 4.10 (1H, d,
J=8.6), 2.44 (3H, d, J=10.6), 2.20 (3H, d, J=9.9).
Finally 5 was prepared from 9 as described for 4 in 84%
yield; [h]2D0=−18.0 (c 0.155, CHCl3) [cf. lit.3f [h]2D0=
−18.0 (c 1.0, CHCl3)]; lH (270 MHz, CDCl3) 7.16–7.09
(6H, m), 7.05–7.02 (4H, m), 3.57 (2H, s), 2.47 (2H, bs),
2.26 (6H, s).
3.4. (R3a,R7a)-1,3-(Dimethyl)-2-phenyl-2,3,3a,4,5,6,7,7a-
octahydro-1H-1,3,2-benzodiazaphosphole 2-oxide 8
Acknowledgements
Compound 6 (1.0 g, 4.24 mmol) was dissolved in THF
(20.0 mL) and cooled to 0°C. n-BuLi (3.4 mL, 8.53
mmol of 2.5 M solution in hexanes) was added drop-
wise. The resulting orange solution was stirred for 1 h
before dropwise addition of methyl iodide (0.53 mL,
8.52 mmol). After 1.5 h at room temperature the reac-
tion was quenched by the addition of water and the
aqueous extracted with DCM (3×20 mL). The com-
bined organics were dried over sodium sulfate, filtered
and solvent evaporated to give 8 as a white solid (1.15
g, 100%); [h]D20=−29.5 (c 0.9, CHCl3); wmax (CHCl3 film)
1441 (PꢀAr), 1250 (PꢁO) cm−1; lH (270 MHz, CDCl3)
7.80–7.72 (2H, m), 7.54–7.41 (3H, m), 2.97–2.89 (1H,
m), 2.66–2.53 (4H, m), 2.28 (3H, d, J=11.2), 2.12 (1H,
m), 2.01–1.98 (1H, m), 1.88–1.85 (4H, m), 1.39–1.21
(4H, m); lC (100 MHz, CDCl3) 132.7 (CH), 131.5
(CH), 130.0 (Ci ), 128.3 (CH), 65.5 (CH), 63.7 (CH),
28.8 (CH3), 28.3 (CH2), 24.4 (CH2); lP (160 MHz,
CDCl3) 34.1 (s); m/z (CI) 265 (MH+, 100%); (found:
265.146084. C14H21N2OP requires MH, 265.146977).
We thank the EPSRC and Glaxo-SmithKline Research
and Development for support of an Industrial CASE
studentship (to HT) and Professor D. Games and Dr.
B. Stein of the EPSRC National Mass Spectroscopic
service (Swansea) for HRMS analysis of certain com-
pounds. We wish to acknowledge the use of the
EPSRCs Chemical Database Service at Daresbury.9
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