1004
A. Korostylev et al. / Tetrahedron: Asymmetry 15 (2004) 1001–1005
conversion of the prochiral substrates and the ees were
determined by GC (AMe: Lipodex E, 25 m · 0.25 mm,
145 ꢁC, 1 mL/min; ItMe2: Lipodex E, 25 m · 0.25 mm,
80 ꢁC, 1 mL/min).
C27H15Br2O4P (594.2); MS (EI, 70 eV): 594 (11) [M]þ,
489 (4), 105 (100).
4.5. (R)-Benzoyl-(3,30-dimethyl-1,10-binaphthyl-2,20-
diyl)phosphite 3d
4.2. (R)-Acetyl-(1,10-binaphthyl-2,20-diyl)phosphite 3a
Application of the same method as detailed above for
the synthesis of 3a, starting from chlorophosphite 2c
(1.32 g, 3.5 mmol) and sodium benzoate (0.72 g,
A solution of chlorophosphite 2a (1.225 g, 3.5 mmol) in
THF (15 mL) was added to a warm (45 ꢁC) suspension
of sodium acetate (0.41 g, 5.0 mmol) in THF (15 mL)
and the resulting mixture then stirred at the same tem-
perature for 4 h. The solvent was removed under
reduced pressure, the residue dissolved in toluene
(40 mL), filtered through celite and the obtained filtrate
5.0 mmol). White solid, 1.32 g (81 % yield). Mp 128 ꢁC.
25
½aꢀ ¼ )351.4 (c 0.46, CH2Cl2). 31P NMR (CDCl3): d
D
1
138.8. H NMR (CDCl3): d 7.86–7.93 (m, 2H), 7.75–
7.84 (m, 4H), 7.52 (m, 1H), 7.37 (m, 4H), 7.10–7.26 (m,
4H), 2.60 (s, 3H), 2.49 (s, 3H). IR (KBr): m (C@O)
1720 cmꢁ1. C29H21O4P (464.1) MS (EI, 70 eV): 464 (40)
[M]þ, 360 (31), 105 (100).
concentrated in vacuum to give a white amorphous solid
23
D
(1.15 g, 88% yield). Mp 72 ꢁC. ½aꢀ ¼ )463.6 (c 1.07,
CH2Cl2). IR (KBr): m (C@O) 1736 cmꢁ1
.
31P NMR
(CDCl3): d 142.0. 13C NMR (CDCl3): 21.0 (CH3), 120.1
(CH), 120.5 (CH), 121.8 (C), 123.3 (C), 124.2, 124.4,
125.4, 125.5, 125.9, 127.3, 127.4, 129.0, 129.7 (all CH),
130.3, 130.7, 131.5, 131.7 (all C), 145.5 (d, JC;P ¼ 1:9 Hz,
4.6. (R)-Benzoyl-(3,30-diphenyl-1,10-binaphthyl-2,20-
diyl)phosphite 3e
CO), 146.4 (d, JC;P ¼ 3:8 Hz, CO), 168.8 (d, JC;P
¼
¼
Application of the same method as detailed above for the
synthesis of 3a, starting from chlorophosphite 2d (1.76 g,
3.5 mmol) and sodium benzoate (0.72 g, 5.0 mmol). Beige
4:8 Hz, COO). 1H NMR (CDCl3): d 2.05 (d, JH;P
1:0 Hz, 3H, CH3), 7.20 (m, 2H), 7.30 (m, 3H), 7.38 (m,
2H), 7.48 (d, J ¼ 8:6 Hz, 1H), 7.89 (m, 4H). MS (EI,
70 eV): 374 (81) [M]þ, 332 (100), 268 (13). Found: C
70.60, H 4.53. Calcd for C22H15O4P: C 70.59, H 4.04.
25
solid, 1.85 g (90 % yield). Mp 103 ꢁC. ½aꢀ ¼ )324.7 (c
D
0.38, CH2Cl2). 31P NMR (CDCl3): d 138.8. IR (KBr): m
(C@O) 1718 cmꢁ1. C39H25O4P (588.1); MS (EI, 70 eV):
588 (36) [M]þ, 483 (28), 105 (100).
4.3. (R)-Benzoyl-(1,10-binaphthyl-2,20-diyl)phosphite 3b
4.7. (R)-Benzoyl-[3,30-bis(trimethylsilyl)-1,10-binaphthyl-
2,20-diyl]phosphite 3f
Application of the same method as detailed above for
the synthesis of 3a, using sodium benzoate (0.72 g,
5.0 mmol). White solid, 1.32 g (87% yield). Mp 125 ꢁC.
Application of the same method as detailed above for
the synthesis of 3a, starting from chlorophosphite 2e
(1.73 g, 3.5 mmol) and sodium benzoate (0.72 g,
5.0 mmol). White solid, 1.685 g (83% yield). Mp 111 ꢁC.
31P NMR (CDCl3): d 143.1. C33H33O4PSi2 (580.2); MS
(EI, 70 eV): 508 (51) [M)SiMe3]þ, 105 (100).
21
½aꢀ ¼ )371.0 (c 0.5, CH2Cl2). 31P NMR (CDCl3): d
D
142.8. 13C NMR (CDCl3): d 121.8 (CH), 122.1 (CH),
123.5 (d, JC;P ¼ 1:9 Hz, C), 124.8 (d, JC;P ¼ 5:7 Hz, C),
125.7, 125.9, 127.5, 128.81, 128.89, 128.95, 129.0 (all
CH), 129.3 (d, JC;P ¼ 2:9 Hz, C), 130.6, 130.9, 131.3 (all
CH), 131.9, 132.3, 133.1, 133.3 (all C), 134.6 (CH),
147.20 (d, JC;P ¼ 1:9 Hz, CO), 148.2 (d, JC;P ¼ 4:8 Hz,
1
CO), 165.6 (d, JC;P ¼ 6:7 Hz, COO). H NMR (CDCl3):
4.8. Preparation of Rh complexes with ligands 3a–f
(general procedure)
d 7.15–7.25 (m, 2H), 7.28–7.41 (m, 7H), 7.45–7.55 (m,
2H), 7.82–7.95 (m, 6H). IR (KBr): m (C@O) 1716 cmꢁ1
.
MS (EI, 70 eV): 436 (100) [M]þ, 331 (12), 268 (15), 239
(12), 105 (100). EI-HRMS (70 eV): 436.0842 (calcd for
C27H17O4P: 436.0865). Found: C 74.24, H 4.45. Calcd
for C27H17O4P: C 74.31, H 3.93.
A solution of the relevant ligand (0.3 mmol) in CH2Cl2
(10 mL) was added dropwise to a stirred solution of
[Rh(COD)2]BF4 (0.061 g, 0.15 mmol) in CH2Cl2 (20 mL)
at 20 ꢁC. The reaction mixture was stirred for 30 min
and aliquots taken for use in catalysis. In order to isolate
solid complexes, the solution was concentrated in vac-
uum and 10 mL of hexane then added to the residue.
The obtained solid rhodium products were washed with
hexane (2 · 10 mL) and dried in vacuum.
4.4. (R)-Benzoyl-(3,30-dibromo-1,10-binaphthyl-2,20-
diyl)phosphite 3c
Application of the same method as detailed above for
the synthesis of 3a, starting from chlorophosphite 2b
(1.78 g, 3.5 mmol) and sodium benzoate (0.72 g,
4.8.1. [Rh(COD)(3b)2]BF4. Yellow solid, 0.137 g (73%
yield). Mp >300 ꢁC. 31P NMR (CDCl3): d 135.2 (d,
5.0 mmol). Beige solid, 1.77 g (85% yield). Mp 113 ꢁC.
23
½aꢀ ¼ )375.3 (c 0.64, CH2Cl2). 31P NMR (CDCl3): d
1
1JP;Rh ¼ 258:0 Hz). H NMR (CDCl3): d 1.61 (m, 2H),
D
1
142.6. H NMR (CDCl3): d 8.33 (s, 1H), 8.29 (s, 1H),
8.03 (m, 2H), 7.87 (m, 2H), 7.59 (m, 1H), 7.40–7.52 (m,
2.18 (m, 2H), 2.60 (m, br, 4H), 4.35 (m, 2H), 6.36 (m,
2H), 7.28–7.44 (m, 14H), 7.48 (m, 2H), 7.55–7.67 (m,
4H), 7.91 (m, 8H), 8.10 (m, 4H), 8.29 (d, J ¼ 8:9 Hz,
5H), 7.26–7.33 (m, 3H). IR (KBr): m (C@O) 1720 cmꢁ1
.