Y.-Y. Chen et al. / Tetrahedron: Asymmetry 23 (2012) 904–909
907
4.2.2.2. (R)-3,30-Dinaphthyl-1,10-Binaphthyl-2,20-diyl phospho-
4.2.3.4. (R,R)-1d.
White solid, 71% yield; mp 283–284 °C;
ramide 5d.
White solid, 90% yield; mp 245–246 °C;
½
a 2D0
ꢂ
¼ ꢁ94:2 (c 1, THF) ; 1H NMR (300 MHz, DMSO-d6) d 8.23–
½
a 2D0
ꢂ
¼ ꢁ180:8 (c 1, THF); 1H NMR (300 MHz, DMSO-d6) d 8.23–
6.92 (m, 46H), 6.68–6.60 (m, 1H), 5.99 (d, J = 7.0 Hz, 1H); 13C
NMR (75 MHz, DMSO-d6) d 146.9, 146.7, 146.2, 134.7, 134.6,
134.2, 134.0, 133.4, 133.2, 133.1, 132.9, 132.7, 132.5, 132.4,
132.3, 132.2, 132.1, 131.9, 131.8, 131.7, 131.4, 131.3, 131.0,
130.8, 130.7, 130.6, 130.0, 128.8, 128.6, 128.4, 128.1, 127.7,
127.3, 127.2, 126.9, 126.7, 126.5, 126.3, 126.2, 125.8, 125.5,
124.9, 123.0, 122.3, 122.1; 31P NMR (162 MHz, DMSO-d6) d ꢁ0.8;
8.08 (m, 4H), 8.06–7.91 (m, 4H), 7.80–7.30 (m, 16H); 13C NMR
(75 MHz, DMSO-d6) d 145.6, 145.4, 144.7, 144.6, 135.3, 134.5,
133.1, 132.8, 132.7, 132.7, 132.6, 132.5, 132.5, 132.3, 132.0,
131.9, 131.8, 131.7, 131.6, 131.0, 130.8, 128.7, 128.6, 128.5,
128.2, 128.0, 127.8, 127.1, 126.9, 126.4, 126.2, 126.0, 125.7,
125.6, 125.6, 125.5, 125.3, 125.2, 121.9, 121.3; FT-IR (KBr)
m
3059, 2928, 1540, 1514, 1461, 1291, 970, 859, 773 cmꢁ1; HRMS(E-
FT-IR (KBr)
891, 776, 750 cmꢁ1
([M+H]+): 1182.3108, found: 1182.3108.
m
3051, 2956, 2860, 1509, 1445, 1388, 1203, 954,
SI+) m/z calcd for
C
40H27NO3P ([M+H]+): 600.1723, found:
;
HRMS(ESI+) m/z calcd for C80H50NO6P2
600.1719.
4.2.3. Double axially chiral catalysts (R,R)-1
4.2.3.5. (R,R)-1e.
Synthesized by using (R)-1,10-binaphthyl-
To a stirred solution of (R)-1,10-binaphthyl-3,30-diaryl phos-
phoryl chloride (1.3 mmol) in dry DMF (10 mL) was added NaH
(80% in oil, 4 mmol) under a nitrogen atmosphere at room temper-
ature. After stirring for 5 min, (R)-1,10-binaphthyl-3,30-diaryl phos-
phoramide (1 mmol) was added in one portion and the mixture
was stirred for another 1 h. After the reaction was complete,
30 mL of CH2Cl2 was added to the flask and the mixture was
washed with saturated brine (50 mL ꢀ 5). The organic layer was
dried over Na2SO4 and concentrated under reduced pressure. The
crude product was purified with silica gel column chromatography
(CH2Cl2/CH3OH = 20:1). The product was then successively dis-
solved in CH2Cl2, acidified with 4 M HCl (10 mL), washed with
brine (20 mL ꢀ 2), dried over Na2SO4, and concentrated in vacuo
to give catalyst (R,R)-1.
3,30-diphenyl phosphoryl chloride and (R)-1,10-binaphthyl-3,30-di-
[3,5-bis(trifluoromethyl)]phenyl phosphoramide. White solid,
74% yield; mp 294–295 °C; ½a D20
ꢂ
¼ ꢁ307:0 (c 1, THF) ; 1H NMR
(300 MHz, DMSO-d6)
d 8.45 (s, 2H), 8.35 (s, 1H), 8.17 (d,
J = 8.3 Hz, 1H), 8.13–7.91 (m, 4H), 7.91–7.72 (m, 5H), 7.72–6.92
(m, 20H), 6.92–6.69 (m, 3H); 13C NMR (75 MHz, DMSO-d6) d
146.5, 146.5, 146.4, 146.4, 146.3, 146.1, 146.0, 145.9, 145.9,
140.1, 139.9, 137.4, 136.9, 133.9, 133.5, 132.3, 132.1, 131.5,
131.1, 131.1, 131.0, 130.8, 130.7, 130.2, 130.1, 130.0, 129.8,
129.8, 129.7, 129.6, 129.2, 129.1, 129.1, 128.7, 128.3, 128.2,
127.3, 126.7, 126.6, 126.1, 125.8, 125.5, 125.2, 125.0, 124.6,
124.5, 122.8, 122.6, 122.3, 121.6, 121.3, 120.5, 119.9, 118.0,
117.7; 31P NMR (162 MHz, DMSO-d6) d 0.4, ꢁ3.0; FT-IR (KBr)
m
3059, 2928, 2843, 1507, 1382, 1376, 1278, 1180, 1134, 997, 892,
747, 682 cmꢁ1
([M+H]+): 1254.1977, found: 1254.1974.
; HRMS(ESI+) m/z calcd for C68H38F12NO6P2
4.2.3.1. (R,R)-1a.
White solid, 79% yield; mp 260–261 °C;
½
a 2D0
ꢂ
¼ ꢁ99:6 (c 1, THF) ; 1H NMR (300 MHz, DMSO-d6) d 8.22–
8.10 (m, 2H), 8.10–8.02 (m, 2H), 8.02–7.94 (m, 2H), 7.94–7.84
(m, 2H), 7.65–7.54 (m, 2H), 7.54–7.38 (m, 6H), 7.38–7.16 (m,
8H); 13C NMR (75 MHz, DMSO-d6) d 148.7, 148.6, 148.6, 148.1,
131.7, 131.6, 130.7, 130.6, 130.4, 130.2, 130.2, 128.4, 126.4,
126.2, 126.0, 126.0, 125.0, 124.9, 121.9, 121.6, 121.1; FT-IR (KBr)
4.2.3.6. (R,R)-1f.
Synthesized by using (R)-1,10-binaphthyl-
3,30-diphenyl phosphoryl chloride and (R)-1,10-binaphthyl-,30-di-
(3,5-dimethylphenyl) phosphoramide. White solid, 72% yield; mp
321–322 °C;
½
a 2D0
ꢂ
¼ ꢁ258:0 (c 1, THF)
;
1H NMR (300 MHz,
DMSO-d6) d 8.17–8.05 (m, 6H), 8.02–7.86 (m, 3H), 7.56–7.41 (m,
7H), 7.41–7.31 (m, 5H), 7.31–7.21 (m, 4H), 7.21–6.98 (m, 7H),
6.66 (t, J = 7.4 Hz, 1H), 6.52–6.41 (m, 3H), 2.34 (s, 6H), 1.68 (s,
6H); 13C NMR (75 MHz, DMSO-d6) d 146.8, 146.7, 146.6, 137.4,
137.0, 136.9, 136.7, 135.7, 134.0, 131.8, 131.7, 131.6, 131.5,
130.4, 130.3, 130.2, 130.1, 130.1, 129.7, 129.6, 129.4, 128.3,
128.2, 128.0, 127.8, 127.5, 126.9, 126.7, 126.1, 126.0, 125.9,
124.8, 124.5, 21.0, 20.3; 31P NMR (162 MHz, DMSO-d6) d 3.7, 1.2;
m
2923, 1505, 1591, 1621, 1451, 1213, 1146, 975, 988, 885 cmꢁ1
;
HRMS(ESI+) m/z calcd for C40H26NO6P2 ([M+H]+): 678.1230, found:
678.1227.
4.2.3.2. (R,R)-1b.
White solid, 84% yield; mp 253–254 °C.
½
a 2D0
ꢂ
¼ ꢁ175:6 (c 1, THF); 1H NMR (300 MHz, DMSO-d6) d 8.27–
7.89 (m, 10H), 7.61–6.97 (m, 24H), 6.82 (t, J = 7.5 Hz, 2H), 6.63 (t,
J = 7.6 Hz, 4H); 13C NMR (75 MHz, DMSO-d6) d 146.5, 146.4,
146.3, 137.3, 137.0, 134.2, 133.9, 131.7, 131.6, 130.2, 129.8,
129.5, 128.3, 128.2, 127.7, 126.9, 126.7, 126.0, 125.9, 125.8,
124.8, 124.7, 122.6, 122.2; 31P NMR (162 MHz, DMSO-d6) d 2.2;
FT-IR (KBr)
m
3049, 2916, 1600, 1502, 1359, 1209, 971, 891, 842,
751 cmꢁ1
;
HRMS(ESI+) m/z calcd for C68H50NO6P2 ([M+H]+):
1038.3108, found: 1038.3110.
FT-IR (KBr)
m
3066, 2966, 2930, 1646, 1571, 1422, 1136, 994,
4.3. General experimental procedures for the asymmetric Man-
nich reaction and characterization data for compounds 9a–m
957, 858 cmꢁ1; HRMS(ESI+) m/z calcd for C64H42NO6P2 ([M+H]+):
982.2482, found: 982.2485.
To
a
suspension of aniline (0.2 mmol), benzaldehyde
4.2.3.3. (R,R)-1c.
Synthesized by using (R)-1,10-binaphthyl-
(0.22 mmol) and 5 Å molecular sieves (90 mg) in 1.5 mL of dry tol-
uene in a vial were added 1d (0.004 mmol). After stirring at room
temperature for 0.5 h, cyclohexanone (8 mmol) was added to the
mixture. The reaction was completed in 12 h and the resulting
mixture was concentrated under reduced pressure. The residue
was purified with silica gel column chromatography (petroleum
ether/ethyl acetate = 8:1) to give pure product 7.
3,30-diphenyl phosphoryl chloride and (R)-1,10-binaphthyl-3,30-
dinaphthyl phosphoramide 5d. White solid, 75% yield; mp 233–
234 °C; ½a 2D0
ꢂ
¼ ꢁ204:6 (c 1, THF); 1H NMR (300 MHz, DMSO-d6) d
8.25–7.66 (m, 14H), 7.66–7.02 (m, 25H), 6.99–6.89 (m, 2H), 6.59–
6.38 (m, 2H), 6.38–6.19 (m, 1H); 13C NMR (75 MHz, DMSO-d6) d
147.3, 147.2, 146.7, 146.4, 137.6, 136.7, 134.7, 134.6, 134.5,
133.3, 132.5, 132.3, 132.2, 132.1, 131.9, 131.8, 131.6, 131.0,
130.7, 130.4, 130.3, 130.0, 129.8, 129.7, 129.5, 129.1, 128.5,
128.4, 128.3, 128.2, 128.0, 127.9, 127.4, 127.1, 126.8, 126.5,
126.2, 126.1, 125.7, 125.6, 125.4, 125.2, 125.0, 124.7, 122.7,
4.3.1. (R)-2-((R)-(4-
Nitrophenyl)(phenylamino)methyl)cyclohexanone 9a3i,11
Yield: 99%; syn/anti: >99/1; 99% ee (Daicel Chirapak AD-H, hex-
ane/isopropanol = 70/30, flow rate 1.0 mL/min, tR (major) = 7.666 -
122.0; 31P NMR (162 MHz, DMSO-d6) d 1.2, ꢁ0.3; FT-IR (KBr)
m
;
3054, 2923, 2851, 1594, 1502, 1201, 959, 887, 776, 749 cmꢁ1
min, tR (minor) = 10.600 min); ½a D20
ꢂ
¼ þ37:4 (c 1, CHCl3); 1H NMR
HRMS(ESI+) m/z calcd for
found: 1082.2799.
C
72H46NO6P2 ([M+H]+):1082.2795,
(300 MHz, DMSO-d6) d 8.14 (d, J = 8.7 Hz, 2H), 7.65 (d, J = 8.7 Hz,
2H), 7.06–6.91 (m, 2H), 6.62–6.41 (m, 3H), 4.94 (t, J = 6.5 Hz, 1H),