Novel Chiral Phase-Transfer Catalysts
A R T I C L E S
CDCl3) δ 152.3, 137.0, 133.1, 128.3, 126.1, 125.8, 125.6, 125.5, 123.7,
108.8, 13.3 ppm; IR (KBr) 3385, 1622, 1601, 1570, 1508, 1437, 1383,
1331, 1234, 1161, 1101, 862, 748 cm-1. HRMS (ESI) Calcd for
C22H17O2: 313.1223 ([M - H]-), found: 313.1206 ([M - H]-). Anal.
Calcd for C22H18O2: C, 84.05; H, 5.77; O, 10.18. Found: C, 83.88; H,
1528, 1420, 1362, 1240, 1042, 866, 816, 754, 709 cm-1. HRMS (FAB)
Calcd for C34H20F6: 542.1469 (M+), found: 542.1479 (M+). Anal.
Calcd for C34H20F6: C, 75.27; H, 3.72; F, 21.01. Found: C, 75.45; H,
3.54; F, 20.73. Mp 309 °C. [R]27 -58.8° (c 0.50, CHCl3).
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(S)-3,3′-Bis(3,5-diphenylphenyl)-2,2′-bis(bromomethyl)-1,1′-bi-
naphthyl [(S)-23 (Ar ) 3,5-Ph2-Ph)]. Radical bromination of (S)-22
(Ar ) 3,5-Ph2-Ph) was performed as described before. The residual
crude product was purified by column chromatography on silica gel
(CH2Cl2/hexane ) 1:20 as eluant) to afford (S)-3,3′-bis(3,5-diphen-
ylphenyl)-2,2′-bis(bromomethyl)-1,1′-binaphthyl [(S)-23 (Ar ) 3,5-Ph2-
Ph)] (97% yield): 1H NMR (400 MHz, CDCl3) δ 8.04 (2H, s, Ar-H),
7.94 (2H, d, J ) 8.4 Hz, Ar-H), 7.91 (2H, t, J ) 1.6 Hz, Ar-H), 7.87
(2H, s, Ar-H), 7.86 (2H, s, Ar-H), 7.74-7.77 (8H, m, Ar-H), 7.54
(2H, ddd, J ) 8.4, 7.2, 1.2 Hz, Ar-H), 7.46-7.49 (8H, m, Ar-H),
7.36-7.40 (4H, m, Ar-H), 7.33 (2H, ddd, J ) 8.4, 7.2, 1.2 Hz, Ar-
5.99; O, 10.09. Mp 202 °C. [R]27 -16.8° (c 0.50, CHCl3).
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Trifluoromethanesulfonylation of (S)-29 was performed as described
before. Purification of the crude product by column chromatography
on silica gel (CH2Cl2/hexane ) 1:5 as eluant) gave (S)-3,3′-bis-
(trifluoromethanesulfonyloxy)-2,2′-dimethyl-1,1′-binaphthyl [(S)-30]
(95% yield): 1H NMR (300 MHz, CDCl3) δ 7.96 (2H, d, J ) 8.4 Hz,
Ar-H), 7.94 (2H, s, Ar-H), 7.54 (2H, ddd, J ) 8.4, 6.9, 1.2 Hz, Ar-
H), 7.34 (2H, ddd, J ) 8.4, 6.9, 1.2 Hz, Ar-H), 6.99 (2H, d, J ) 8.4
Hz, Ar-H), 2.04 (6H, s, Ar-CH3) ppm; 13C NMR (100 MHz, CDCl3)
δ 146.9, 137.4, 132.1, 131.5, 128.3, 128.3, 127.8, 127.0, 125.3, 119.6,
118.9 (q, JC-F ) 317 Hz), 13.9 ppm; IR (KBr) 3067, 1564, 1504, 1420,
H), 7.22 (2H, d, J ) 8.8 Hz, Ar-H), 4.38 (4H, s, Ar-CH2) ppm; 13
C
1323, 1248, 1225, 1140, 1053, 988, 922, 881, 819, 779, 754 cm-1
.
NMR (100 MHz, CDCl3) δ 141.5, 141.3, 140.8, 140.7, 136.4, 133.1,
132.2, 131.9, 130.4, 128.8, 127.9, 127.5, 127.3, 126.6, 125.2, 32.2 ppm;
IR (KBr) 3443, 3057, 2924, 1593, 1497, 1406, 1217, 1028, 885, 758,
696 cm-1. HRMS (FAB) Calcd for C58H40Br2: 894.1497 (M+), found:
HRMS (ESI) Calcd for C24H15F6O6S2: 577.0209 ([M - H]-), found:
577.0223 ([M - H]-). Anal. Calcd for C24H16F6O6S2: C, 49.83; H,
2.79; F, 19.70. Found: C, 49.79; H, 2.88; F, 19.90. Melted around
room temperature. [R]27 -20.9° (c 0.58, CHCl3).
894.1464 (M+). Mp 185 °C. [R]27 -37.2° (c 0.50, CHCl3).
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(S)-3,3′-Bis(3,5-diphenylphenyl)-2,2′-dimethyl-1,1′-binaphthyl [(S)-
22 (Ar ) 3,5-Ph2-Ph)]. A mixture of (S)-30 (289 mg, 0.50 mmol),
3,5-diphenylphenylboronic acid (329 mg, 1.2 mmol), Pd(OAc)2 (5.8
mg, 5 mol %), triphenylphosphine (29.4 mg, 0.11 mmol), and K3PO4‚
nH2O (429 mg, 1.5 mmol) in THF (5 mL) was heated to 65 °C and
stirred for 12 h under argon atmosphere. The resulting mixture was
poured into saturated NH4Cl, and the whole mixture was filtered to
remove the catalyst. The filtrate was extracted with ethyl acetate. The
organic extracts were dried over Na2SO4 and concentrated. The residue
was purified by column chromatography on silica gel (CH2Cl2/hexane
) 1:20 as eluant) to afford (S)-3,3′-bis(3,5-diphenylphenyl)-2,2′-
dimethyl-1,1′-binaphthyl [(S)-22 (Ar ) 3,5-Ph2-Ph)] (336 mg, 0.45
mmol, 91% yield): 1H NMR (400 MHz, CDCl3) δ 7.97 (2H, s, Ar-
H), 7.92 (2H, d, J ) 8.0 Hz, Ar-H), 7.84 (2H, t, J ) 1.6 Hz, Ar-H),
7.70-7.74 (12H, m, Ar-H), 7.43-7.49 (10H, m, Ar-H), 7.38 (4H,
ddt, J ) 7.6, 6.4, 1.2 Hz, Ar-H), 7.28 (2H, ddd, J ) 8.4, 6.8, 1.2 Hz,
Ar-H), 7.17 (2H, d, J ) 8.0 Hz, Ar-H), 2.08 (6H, s, Ar-CH3) ppm;
13C NMR (100 MHz, CDCl3) δ 143.2, 141.6, 141.0, 141.0, 136.6, 132.5,
132.1, 132.0, 128.7, 128.3, 127.9, 127.4, 127.3, 126.2, 125.7, 125.4,
124.7, 18.5 ppm; IR (KBr) 3443, 3053, 2364, 1593, 1497, 1406, 1030,
881, 758, 698 cm-1. HRMS (FAB) Calcd for C58H42: 738.3287 (M+),
found: 738.3283 (M+). Anal. Calcd for C58H42: C, 94.27; H, 5.73.
Found: C, 94.33; H, 5.87. Mp 170 °C. [R]27D -50.4° (c 0.50, CHCl3).
(S)-3,3′-Bis(4-fluorophenyl)-2,2′-dimethyl-1,1′-binaphthyl [(S)-22
(Ar ) 4-F-Ph)]: (95% yield): 1H NMR (400 MHz, CDCl3) δ 7.89
(2H, d, J ) 8.4 Hz, Ar-H), 7.82 (2H, s, Ar-H), 7.41-7.47 (6H, m,
Ar-H), 7.25 (2H, ddd, J ) 8.4, 6.8, 1.2 Hz, Ar-H), 7.12-7.18 (4H,
m, Ar-H), 7.09 (2H, d, J ) 8.0 Hz, Ar-H), 1.92 (6H, s, Ar-CH3)
ppm; 13C NMR (100 MHz, CDCl3) δ 161.9 (d, JC-F ) 246 Hz), 140.1,
(S)-3,3′-Bis(4-fluorophenyl)-2,2′-bis(bromomethyl)-1,1′-binaph-
thyl [(S)-23 (Ar ) 4-F-Ph)]: (98% yield): 1H NMR (400 MHz, CDCl3)
δ 7.91 (2H, d, J ) 8.0 Hz, Ar-H), 7.89 (2H, s, Ar-H), 7.56-7.61
(4H, m, Ar-H), 7.52 (2H, ddd, J ) 8.0, 6.8, 1.2 Hz, Ar-H), 7.30
(2H, ddd, J ) 8.4, 6.8, 1.2 Hz, Ar-H), 7.14-7.20 (6H, m, Ar-H),
4.23 (4H, s, Ar-CH2) ppm; 13C NMR (100 MHz, CDCl3) δ 163.7 (d,
JC-F ) 247 Hz), 139.8, 136.2, 136.2 (d, JC-F ) 3.3 Hz), 133.0, 132.2,
131.8, 131.1 (d, JC-F ) 7.4 Hz), 130.5, 127.8, 127.3, 127.2, 126.6,
115.1 (d, JC-F ) 21.5 Hz), 32.0 ppm; IR (KBr) 3061, 1603, 1510,
1219, 1157, 1094, 1026, 968, 893, 843, 750 cm-1. HRMS (FAB) Calcd
for C34H22Br2F2: 626.0056 (M+), found: 626.0051 (M+). Anal. Calcd
for C34H22Br2F2: C, 64.99; H, 3.53; Br, 25.43; F, 6.05. Found: C, 64.53;
H, 3.55; Br, 25.98; F, 6.23. Mp 218 °C. [R]27D -73.2° (c 0.50, CHCl3).
(S)-3,3′-Bis(3,4,5-trifluorophenyl)-2,2′-bis(bromomethyl)-1,1′-bi-
naphthyl [(S)-23 (Ar ) 3,4,5-F3-Ph)]: (quantitative yield): 1H NMR
(300 MHz, CDCl3) δ 7.94 (2H, d, J ) 8.1 Hz, Ar-H), 7.89 (2H, s,
Ar-H), 7.57 (2H, ddd, J ) 8.1, 6.9, 1.2 Hz, Ar-H), 7.34 (2H, ddd,
J ) 8.1, 6.9, 1.2 Hz, Ar-H), 7.25-7.30 (4H, m, Ar-H), 7.13 (2H, d,
J ) 8.1 Hz, Ar-H), 4.19 (4H, s, Ar-CH2) ppm; 13C NMR (100 MHz,
CDCl3) δ 150.7 (ddd, JC-F ) 249, 9.9, 4.1 Hz), 139.4 (dt, JC-F ) 251,
14.9 Hz), 137.7, 136.3, 136.0 (dt, JC-F ) 5.0, 7.9 Hz), 132.9, 132.0,
131.5, 130.6, 128.0, 127.7, 127.3, 127.0, 114.0 (dd, JC-F ) 15.8, 5.8
Hz), 31.1 ppm; IR (KBr) 3441, 3067, 2363, 1614, 1528, 1436, 1367,
1242, 1207, 1045, 868, 752, 712 cm-1. HRMS (FAB) Calcd for C34H18-
Br2F6: 697.9679 (M+), found: 697.9684 (M+). Anal. Calcd for C34H18-
Br2F6: C, 58.31; H, 2.59; Br, 22.82; F, 16.28. Found: C, 58.15; H,
2.43; Br, 22.97; F, 16.48. Mp 239 °C. [R]27D -63.8° (c 0.50, CHCl3).
Chiral Ammonium Salt (S,S)-11d. (S,S)-11d was prepared in a
manner similar to that described for the preparation of (S,S)-11a. (72%
yield): 1H NMR (400 MHz, CDCl3) δ 8.60 (2H, br, Ar-H), 8.47 (2H,
s, Ar-H), 8.18 (2H, s, Ar-H), 8.14 (2H, d, J ) 8.4 Hz, Ar-H), 8.06
(4H, br, Ar-H), 7.75 (2H, d, J ) 8.4 Hz, Ar-H), 7.65 (2H, t, J ) 7.2
Hz, Ar-H), 7.43 (2H, t, J ) 7.2 Hz, Ar-H), 7.35-7.39 (4H, m, Ar-
H), 7.21 (2H, d, J ) 8.8 Hz, Ar-H), 7.14 (2H, t, J ) 7.2 Hz, Ar-H),
7.1-7.8 (18H, br, Ar-H), 7.06 (2H, d, J ) 8.8 Hz, Ar-H), 6.57 (2H,
d, J ) 8.8 Hz, Ar-H), 5.06 (2H, d, J ) 14.0 Hz, Ar-CH2), 4.39 (2H,
d, J ) 14.0 Hz, Ar-CH2), 4.34 (2H, d, J ) 13.2 Hz, Ar-CH2), 3.68
(2H, d, J ) 13.2 Hz, Ar-CH2) ppm; 13C NMR (100 MHz, CDCl3) δ
143.7, 140.4, 139.9, 139.2, 138.8, 136.1, 133.8, 133.7, 132.9, 131.0,
130.8, 128.9, 128.8, 128.5, 128.3, 127.9, 127.8, 127.6, 127.4, 127.3,
127.2, 126.8, 126.6, 126.3, 124.6, 122.2, 62.3, 57.5 ppm; IR (KBr)
3649, 3264, 3055, 1593, 1497, 1454, 1400, 1344, 1306, 1028. 968,
885, 850, 810, 760, 698 cm-1. HRMS (ESI) Calcd for C80H56N:
1030.4407 (M+), found: 1030.4401 (M+). Melted at 252 °C with
138.0 (d, JC-F ) 3.3 Hz), 136.4 132.4, 131.9, 131.9, 131.0 (d, JC-F
)
7.4 Hz), 128.3, 127.8, 126.2, 125.5, 125.4, 114.9 (d, JC-F ) 21.4 Hz),
18.3 ppm; IR (KBr) 3049, 2955, 2924, 1603, 1512, 1425, 1221, 1157,
1094, 1016, 893, 835, 748 cm-1. HRMS (FAB) Calcd for C34H24F2:
470.1846 (M+), found: 470.1841 (M+). Mp 187 °C. [R]27D -69.8° (c
0.50, CHCl3).
(S)-3,3′-Bis(3,4,5-trifluorophenyl)-2,2′-dimethyl-1,1′-binaphthyl
[(S)-22 (Ar ) 3,4,5-F3-Ph)]: (94% yield): 1H NMR (300 MHz, CDCl3)
δ 7.91 (2H, d, J ) 8.1 Hz, Ar-H), 7.82 (2H, s, Ar-H), 7.47 (2H,
ddd, J ) 8.1, 6.9, 1.2 Hz, Ar-H), 7.29 (2H, ddd, J ) 8.1, 6.9, 1.2 Hz,
Ar-H), 7.12 (2H, d, J ) 6.3 Hz, Ar-H), 7.10 (2H, d, J ) 6.3 Hz,
Ar-H), 7.06 (2H, d, J ) 8.1 Hz, Ar-H), 1.91 (6H, s, Ar-CH3) ppm;
13C NMR (100 MHz, CDCl3) δ 150.7 (ddd, JC-F ) 248, 9.9, 4.1 Hz),
139.0 (dt, JC-F ) 250, 15.2 Hz), 138.2, 137.9 (dt, JC-F ) 5.0, 7.5 Hz),
136.5, 132.2, 131.8, 131.7, 128.5, 128.0, 126.9, 125.9, 125.5, 113.7
(dd, JC-F ) 14.9, 5.8 Hz), 18.1 ppm; IR (KBr) 3489, 3067, 2363, 1614,
decomposition. [R]27 -37.4° (c 0.50, CHCl3).
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J. AM. CHEM. SOC. VOL. 125, NO. 17, 2003 5149