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A. Zhang et al. / Tetrahedron: Asymmetry 11 (2000) 3123±3130
3.5. Preparation of compound 10
This compound was prepared according to the literature procedure11 by the reaction of
diamino diol 1 with 2,2-dimethoxypropane and p-methylbenzene sulfonic acid. [ꢁ]D=^25.5 (c 4.0,
1
CHCl3); IR (KBr) 3381, 2986, 2933, 1604, 1495, 1455, 1379, 1246, 1054 cm^1; H NMR (CDCl3,
400 MHz) ꢀ 7.32±7.17 (m, 10H), 4.06 (s, 2H), 3.07 (m, 2H), 2.83 (dd, J=5.0, 13.3 Hz, 2H), 2.64
(dd, J=9.3, 13.3 Hz), 2.4 (brs, 4H), 1.46 (s, 6H); MS (EI) m/z 341 (M++1, 100), 342 (M++2, 31.6),
249 (51.0), 174 (25.4), 130 (19.6), 120 (63.3), 91 (40.4), 72 (23.8). Anal. calcd for C21H28N2O2:
340.3720. Found: 340.3709.
3.6. Typical procedure for the preparation of bisphosphinites 3, 5, 7, 9 and bisaminophosphine 11
To 1.0 equiv. of the corresponding diol 2, 4, 6, 8 or diamine 10 (1.9 mmoL) in CH2Cl2 (20 mL)
were added pyridine (5 mL) and a catalytic amount of DMAP under an argon atmosphere. After
the reaction system was cooled to 0ꢀC, a solution of chlorodiphenylphosphine (937 mg, 4.25 mmoL)
in CH2Cl2 (10 mL) was added dropwise. The reaction mixture was stirred at room temperature
overnight and ®ltered through basic Al2O3 under an argon atmosphere, and the ®ltrate was
evaporated in vacuo to aord bisphosphinites 3, 5, 7, 9 or bisaminophosphine 11 as a viscous
solid (68±80% yield).
Bisphosphinite 3: 73% yield; [ꢁ]D=^12.4 (c 0.5, benzene); ESI (M+1) 726; ꢂmax (neat)/cm^1:
1
3053, 2966, 2831, 1496, 1479, 1454, 1434, 1097, 1027, 736, 697; H NMR (CDCl3) ꢀ 7.25 (m,
30H), 3.92 ( m, 2H, OCH), 3.40 (dd, 2H, J=8.1, 14.2 Hz, NCH), 2.70 (dd, 2H, J=7.8, 14.0 Hz,
CH2Ph), 2.50 (dd, 2H, J=5.4, 14.0 Hz, CH2Ph), 1.67 (s, 12H, NCH3); 31P {1H} NMR ꢀ 101.60 (s).
Bisphosphinite 5: 74% yield; [ꢁ]D=^5.8 (c 0.85, benzene); ESI (M+1) 777; MS (EI) m/z 778
(M++2, 0.67), 591 (M+^PPh2, 1.5), 516 (3.1), 441 (12.4), 400 (11.6), 370 (23.1), 217 (53.4), 200
(20.1), 174 (100); ꢂmax (neat)/cm^1: 2932, 2852, 1602, 1453, 1435, 1262, 1100, 1030, 802, 736, 697;
1H NMR (CDCl3) ꢀ 7.20 (m, 30H), 4.1 (dd, 2H, J=8.47, 8.77, OCH), 3.60 (m, 2H, NCH), 2.70
(dd, 2H, J=6.56, 13.87 Hz), 2.55 (dd, 2H, J=5.6, 14.0 Hz), 2.2 (m, 8H), 1.1 (s, 8H); 31P {1H}
NMR ꢀ 101.57 (s).
Bisphosphinite 7: 68% yield; [ꢁ]D=^21.6 (c 2.6, benzene); ꢂmax (neat)/cm^1: 3054, 2932, 2852,
1600, 1453, 1435, 1262, 1100, 1030, 802, 736, 697; 1H NMR (CDCl3) ꢀ 7.25 (m, 30H), 4.15 (t, 2H,
J=9.14), 3.30 (dd, 2H, J=6.58, 14.38 Hz), 2.80 (dd, 2H, J=7.37, 14.19 Hz), 2.45 (dd, 2H,
J=5.61, 14.16 Hz), 2.30 (m, 2H), 2.15 (m, 2H), 0.9 (m, 8H), 0.7 (m, 4H); 31P {1H} NMR ꢀ 101.97
(s); MS (EI) m/z 806 (M++2, 0.5), 619 (M+^PPh2, 0.3), 458 (21.4), 325 (10.8), 242 (16.1), 217
(50.9), 188 (100), 108 (80.8). Anal. calcd for C40H48N2O2P2 (M+^PPh2): 619.3461. Found:
619.3457.
Bisphosphinite 9: 73% yield; [ꢁ]D=^85.1 (c 2.65, benzene); ꢂmax (neat)/cm^1: 3054, 2932, 2852,
1
1600, 1453, 1435, 1262, 1100, 1030, 802, 736, 697; H NMR (CDCl3) ꢀ 7.50 (m, 40H), 5.25 (s,
2H), 3.10 (m, 4H), 2.95 (m, 4H); MS (EI) m/z 844 (M+, 0.3), 567 (M+^PPh2 5.5), 477 (94.2), 385
(58.7), 282 (28.3), 268 (67.3), 238 (51.5), 208 (51.2), 91 (100). Anal. calcd for C32H31N2O2
(M+^2ÂPPh2): 475.2395. Found: 475.2390.
Bisaminosphosphine 11: 80% yield; [ꢁ]D=37.0 (c 2.17, benzene); ꢂmax (neat)/cm^1: 3375, 3025,
1
2985, 1568, 1496, 1434, 1260, 1094, 741, 697; H NMR (CDCl3) ꢀ 7.20 (m, 30H), 3.85 (m, 2H),
3.45 (m, 2H), 2.75 (dd, 2H, J=8.1, 13.7 Hz), 2.55 (dd, 1H, J=7.0, 13.7 Hz), 2.15 (t, 2H, 10.97),
1.15 (s, 6H); 31P {1H} NMR ꢀ 42.12 (s); MS (EI) m/z 708 (M+, 2.8), 709 (2.6), 617 (6.7), 523
(63.1), 358 (100), 304 (53.71), 201 (38.6), 185 (100), 108 (49.1).