2884
I. H. Escher, A. Pfaltz / Tetrahedron 56 (2000) 2879±2888
(±){2-[(40S)-(40-tert-Butyloxazolin-20-yl)]-2-methylethyl}-
[(R)-(3,30-dimethyl)binaphthyl-2,20-diyl]phosphite (5a).
68% yield, colorless solid, a2D52379.0 (c 0.92, CHCl3).
1H NMR (300 MHz, CDCl3) d 0.89 (s, C(CH3)3, 9H), 1.69
(s, C(CH3)2, 6H), 2.59 (s, Ar(CH3), 6H), 3.93 (dd, J7.3 and
10.1 Hz, CH, 1H), 4.12±4.32 (m, CH2, 2H), 7.12±7.37 (m,
6H), 7.75±7.83 (m, 4H). 13C NMR (75 MHz, CDCl3) d
17.43 (d, J2.1 Hz, Ar(CH3)), 17.95 Ar(CH3), 25.80
C(CH3)3, 28.25 (d, JCP7.7 Hz, C(CH3)2), 28.39 (d,
JCP7.5 Hz, C(CH3)2), 33.87 C(CH3)3, 69.56 CH2, 75.88
CH, 75.90 (d, JCP11.4 Hz, C(CH3)2), 122.88 C, 122.91
C, 124.73 CH, 124.78 CH, 124.86 CH, 125.11 CH, 127.02
CH, 127.07 CH, 127.33 CH, 127.47 CH, 129.18 CH, 129.54
CH, 130.26 C, 130.28 C, 130.78 C, 131.08 C, 131.36 C,
131.48 C, 131.76 C, 147.03 (d, JCP2.5 Hz, C±O), 148.03
(d, JCP5.8 Hz, C±O), 168.34 CvN. 31P NMR (121 MHz,
CDCl3) d 149.3. IR (KBr) n (cm21) 2956, 2869, 1670, 1596,
1477, 1414, 1364, 1334, 1244, 1206, 1148, 1120, 1100,
1095, 980, 957, 901, 881, 860. MS (EI) m/z (rel int%) 527
(M1, 45), 470 (42), 376 (18), 360 (67), 345 (26), 296 (71),
280 (12), 252 (14), 168 (69), 151 (100), 110 (10), 83 (33).
HRMS m/z calculated for C32H34NO4P (M1) 527.2225
found 527.2205. Chlorophosphite intermediate: 31P NMR
(121 MHz, CDCl3) d 175.7.
CH, 127.24 CH, 128.11 CH, 128.20 CH, 128.32 CH, 130.59
CH, 130.27 CH, 130.61 CH, 131.10 C, 131.27 C, 132.32 C,
132.45 C, 134.85 C, 134.90 C, 138.04 C, 138.73 C, 145.13
(d, JCP4.4 Hz, C±O), 145.42 (d, JCP2.0 Hz, C±O),
168.19 CvN. 31P NMR (121 MHz, CDCl3) d 150.7. IR
(KBr) n (cm21) 3054, 2954, 1666, 1409, 1151, 989, 951,
881, 848, 765, 750, 698. MS (EI) m/z (rel int%) 651 (M1,
100), 594 (11), 566 (2), 526 (6), 500 (6), 484 (72), 465 (21),
420 (42), 389 (7), 315 (5), 215 (2), 168 (78), 110 (7), 57
(15). Anal. calcd for C42H38NO4P C, 77.40%; H, 5.88%.
Found C, 77.43%; H, 5.83%.
(+)-{2-[(40S)-(40-tert-Butyloxazolin-20-yl)]-2-methylethyl}-
[(S)-(3,30-diphenyl)binaphthyl-2,20-diyl]phosphite (6b).
89% yield, colorless solid, mp 1218C, a2D01311.7 (c
0.46, CHCl3). 1H NMR (300 MHz, CDCl3) d 0.72
(s, C(CH3)3, 9H), 0.93 (s, CH3, 3H), 1.12 (s, CH3, 3H),
3.57±3.59 (m, 2H), 3.72±3.73 (m, 1H), 7.24±7.38 (m,
4H), 7.40±7.49 (m, 8H), 7.66±7.74 (m, 4H), 7.91±7.95
(m, 2H), 7.97±7.98 (m, 2H). 13C NMR (75 MHz, CDCl3)
d 25.60 C(CH3)3, 26.48 (d, JCP11.9 Hz, C(CH3)2), 27.85
(d, JCP1.3 Hz, C(CH3)2), 33.63 C(CH3)3, 68.89 CH2, 75.43
CH, 75.68 (d, JCP14.0 Hz, C(CH3)2), 124.16 C, 124.19 C,
125.03 CH, 125.31 CH, 125.67 C, 125.75 C, 125.88 CH,
126.11 CH, 127.01 CH, 127.17 CH, 127.97 CH, 128.05 CH,
128.21 CH, 128.32 CH, 130.09 CH, 130.28 CH, 130.51 CH,
131.10 C, 131.22 C, 132.34 C, 132.49 C, 134.84 C, 134.99
C, 138.02 C, 138.68 C, 145.23 (d, JCP2.3 Hz, C±O),
145.50 (d, JCP4.4 Hz, C±O), 168.10 CvN. 31P NMR
(121 MHz, CDCl3) d 150.6. IR (KBr) n (cm21) 3052,
2952, 2363, 1665, 1497, 1454, 1407, 1362, 1247, 1210,
1179, 1153, 1129, 987, 951, 883, 846, 800, 764, 749, 701.
MS (EI) m/z (rel int%) 651 (M1, 100), 594 (10), 526 (6), 501
(9), 484 (66), 465 (18), 420 (48), 389 (7), 315 (5), 215 (1),
168 (41), 110 (7), 57 (24). HRMS m/z calculated for
C42H38NO4P (M1) 651.2538, found 651.2535.
(+){2-[(40S)-(40-tert-Butyloxazolin-20-yl)]-2-methylethyl}-
[(S)-(3,30-dimethyl)binaphthyl-2,20-diyl]phosphite (5b).
26 % yield, colorless solid, a2D51339.1 (c 0.45, CHCl3).
1H NMR (300 MHz, CDCl3) d 0.91 (s, C(CH3)3, 9H), 1.68
(s, C(CH3)2, 3H), 1.69 (s, C(CH3)2, 3H), 2.59 (s, Ar(CH3),
6H), 3.95 (dd, J7.7 and 10.1 Hz, CH, 1H), 4.19 (t,
J8.2 Hz, 1H), 4.28 (dd, J8.7 and 10.1 Hz, 1H), 7.13±
7.36 (m, 5H), 7.75±7.83 (m, 5H). 13C NMR (75 MHz,
CDCl3) d 17.45 (d, J2.3 Hz, Ar(CH3)), 18.01 Ar(CH3),
25.83 C(CH3)3, 28.17 C(CH3)2), 28.29 C(CH3)2), 28.40
C(CH3)2), 33.83 C(CH3)3, 69.56 CH2, 75.86 CH, 75.88 (d,
JCP11.1 Hz, C(CH3)2), 124.59 CH, 124.69 C, 124.77 C,
124.86 CH, 125.11 CH, 127.00 CH, 127.10 CH, 127.33 CH,
127.46 CH, 129.15 CH, 129.53 CH, 130.23 C, 130.26 C,
130.68 C, 131.03 C, 131.33 C, 131.47 C, 131.72 C, 147.01
(d, JCP2.6 Hz, C±O), 148.01 (d, JCP5.3 Hz, C±O),
168.34 CvN. 31P NMR (121 MHz, CDCl3) d 148.9. IR
(KBr) n (cm21) 2955, 2868, 1671, 1502, 1478, 1462,
1414, 1384, 1364, 1334, 1241, 1209, 1148, 1127, 1102,
1085, 980, 954, 907, 881, 862, 803, 767, 747. MS (EI)
m/z (rel int%) 528 (M1, 53), 470 (100), 376 (12), 360
(59), 345 (20), 296 (60), 253 (11), 168 (41), 151 (14), 95
(11), 57 (13). HRMS m/z calculated for C32H34NO4P (M1)
527.2225 found 527.2216.
(±)-{2-[(40S)-(40-tert-Butyloxazolin-20-yl)]-2-methylethyl}-
{(R)-[3,30-bis(4-biphenylyl)](binaphthyl-2,20-diyl} phos-
phite (7a). 48% yield, colorless solid, mp 1258C.
a2D52301.0 (c 0.89, CHCl3). 1H NMR (500 MHz,
CDCl3) d 0.56 (s, C(CH3)3, 9H), 0.89 (s, C(CH3)2, 3H),
1.18 (s, C(CH3)2, 3H), 3.38 (t, J8.2 Hz, 1H), 3.53 (dd,
J10.1 and 7.8 Hz, 1H), 3.72 (dd, J10.1 and 8.7 Hz,
1H), 7.32±7.39 (m, 4H), 7.42±7.51 (m, 6H), 7.61±7.72
(m, 8H), 7.83±7.85 (m, 4H), 7.96±8.00 (m, 3H), 8.06±
8.14 (m, 3H). 13C NMR (75 MHz, CDCl3) d 25.54
C(CH3)3, 26.69 (d, JCP11.3 Hz, C(CH3)2), 27.91 (d,
JCP3.9 Hz, C(CH3)2), 33.54 C(CH3)3, 69.06 CH2, 75.57
CH, 75.85 (d, JCP14.3 Hz, C(CH3)2), 125.14 CH, 125.42
CH, 126.02 CH, 126.24 CH, 126.64 CH, 126.89 CH, 127.07
CH, 127.10 CH, 127.18 CH, 127.26 CH, 127.35 CH, 127.43
CH, 127.51 CH, 128.28 CH, 128.39 CH, 128.76 CH, 128.82
CH, 128.87 CH, 130.02 CH, 130.47 CH, 130.65 CH, 130.75
CH, 131.19 C, 131.39 C, 132.44 C, 132.59 C, 134.53 C,
137.05 C, 137.81 C, 139.91 C, 140.30 C, 140.54 C, 141.01
C, 141.29 C, 145.29 (d, JCP2.2 Hz, C±O), 145.62 (d,
JCP4.9 Hz, C±O), 168.10 CvN. 31P NMR (121 MHz,
CDCl3) d 150.5. IR (KBr) n (cm21) 3054, 3028, 2953,
1666, 1488, 1420, 1396, 1364, 1249, 1196, 1178, 1151,
1132, 1077, 1008, 989, 950, 884, 848, 838, 799, 766, 751,
737, 694. MS (EI) m/z (rel int %) 803 (M1, 84), 746 (12),
653 (10), 636 (100), 617 (25), 572 (54), 555 (3), 544 (5), 483
(±)-{2-[(40S)-(40-tert-Butyloxazolin-20-yl)]-2-methylethyl}-
[(R)-(3,30-diphenyl)binaphthyl-2,20-diyl]phosphite (6a).
89% yield, colorless solid, mp 1068C, a2D52365.6 (c
0.94, CHCl3). 1H NMR (500 MHz, CDCl3) d 0.65 (s,
C(CH3)3, 9H), 0.82 (s, CH3, 3H), 1.14 (s, CH3, 3H), 3.42
(t, J8.1 Hz, 1H), 3.60 (dd, J7.6 and 9.9 Hz, 1H), 3.78
(dd, J8.5 and 9.8 Hz, 1H), 7.23±7.30 (m, 2H), 7.34±7.38
(m, 3H), 7.41±7.47 (m, 7H), 7.71±7.73 (m, 4H), 7.92±7.95
(m, 2H), 7.98±7.99 (m, 2H). 13C NMR (75 MHz, CDCl3) d
25.59 C(CH3)3, 26.56 (d, JCP11.5 Hz, C(CH3)2), 27.83 (d,
JCP3.9 Hz, C(CH3)2), 33.67 C(CH3)3, 69.05 CH2, 75.54
CH, 75.82 (d, JCP14.6 Hz, C(CH3)2), 124.22 CH, 124.26
CH, 125.05 CH, 125.34 CH, 125.92 CH, 126.15 CH, 126.99