1998
Y. B. Kim et al.
LETTER
(15) (a) Kanai, M.; Tomioka, K. Tetrahedron Lett. 1995, 36,
4271. (b) Kanai, M.; Tomioka, K. Tetrahedron Lett. 1995,
36, 4275.
(16) Trost, B. M.; Yeh, V. S. C.; Ito, H.; Bremeyer, N. Org. Lett.
2002, 4, 2621.
Acknowledgment
This work was supported financially by the Center for Molecular
Design & Synthesis (CMDS) and Brain Korea 21.
(17) (a) Kim, Y. H. Acc. Chem. Res. 2001, 34, 955. (b) Kim, S.
M.; Byun, I. S.; Kim, Y. H. Angew. Chem. Int. Ed. 2000, 39,
728.
References
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(18) 2,6-Bis[2-(diphenylphosphinoylmethyl)octahydroindol-
1-ylmethyl]-4-methylphenol(7); Typical Procedure
2,6-Bis(bromomethyl)-4-methylphenol (292 mg, 1 mmol)
was added in one portion to a stirred and cooled solution of
2-(diphenylphosphinoylmethyl)octahydroindole (879 mg, 2
mmol) and K2CO3 (552 mg, 4 mmol) in anhyd DMF (5 mL).
The ice bath was removed after the addition and the resulting
solution was allowed to stir at r.t. for 24 h before it was
diluted with H2O and Et2O. The two phases were separated
and the aqueous phase was extracted with Et2O three times
and the combined organic phases were washed H2O, brine,
dried over MgSO4, and evaporated. The residue was purified
by chromatography through a short slica gel column
(EtOAc–hexane, 1:1) to give 7 in 64% yield (520 mg, yellow
foam). [a]D23 –79.8 (c 1, CHCl3). 1H NMR (300 MHz,
CDCl3): d = 1.42–1.60 (m, 8 H), 1. 65–1.96 (m, 4 H), 2.06
(d, 2 H), 2.08–2.34 (m, 6 H), 2.12 (s, 3 H), 2.36 (t, 2 H),
2.84–2.93 (m, 4 H), 3.28 (d, 2 H), 3.38 (d, 2 H), 3.52 (s, 2 H),
3.96 (s, 2 H), 6.75 (s, 2 H), 7.31–7.38 (m, 10 H), 7.39–7.64
(m, 10 H). 13C NMR (75.5 MHz, CDCl3): d = 20.36, 21.97,
31.34, 31.77, 32.92, 33.63, 52.50, 53.15, 53.54, 59.40,
(7) Effenberger, F.; Stelzer, U. Angew. Chem., Int. Ed. Engl.
1991, 30, 873.
(8) Stelzer, U.; Effenberger, F. Tetrahedron: Asymmetry 1993,
4, 161.
(9) Syed, J.; Furster, S.; Effenberger, F. Tetrahedron:
Asymmetry 1998, 9, 805.
(10) Monterde, M. I.; Brieva, R.; Gotor, V. Tetrahedron:
Asymmetry 2001, 12, 525.
60.00, 123.1, 128.6, 129.6, 129.7, 131.5, 135.0, 155.3. 31
P
NMR (121.5 MHz, CDCl3): d = 29.31 (s). MS (MALDI-
TOF): m/z calcd for C51H60N2O3P2, 810.4079; found,
811.0474.
(19) Asymmetric Cyanosilylation of Aldehydes (Table 4,
entry 2); Typical Procedure
To a solution of 7 (20.2 mg, 0.025 mmol) and O=PPh3 (139
mg, 0.5 mmol) in CH2Cl2 (5 mL), Ti(Oi-Pr)4 (1 M in toluene,
25 mL, 0.025 mmol) was added at r.t., and the mixture was
stirred at 0 °C for 30 min under an argon atmosphere. To this
solution, benzaldehyde (0.25 mol) was added after the
addition of TMSCN (60 mL, 0.5 mmol) in CH2Cl2 (1 mL) at
–20 °C. The reaction was monitored by TLC, after 24 h, the
mixture was concentrated and then purified by silica gel
chromatography (EtOAc–hexane, 1:4) to obtain
(11) Monterde, M. I.; Nazabadioko, S.; Rebolledo, F.; Brieva, R.;
Gotor, V. Tetrahedron: Asymmetry 1999, 10, 3449.
(12) (a) North, M. Synlett 1993, 807. (b) Effenberger, F. Angew.
Chem., Int. Ed. Engl. 1994, 33, 1555. (c) Gregory, R. J. H.
Chem. Rev. 1999, 99, 3649. (d) North, M. Tetrahedron:
Asymmetry 2003, 14, 147.
(13) (a) Ryu, D. H.; Corey, E. J. J. Am. Chem. Soc. 2004, 126,
8106. (b) Ryu, D. H.; Corey, E. J. J. Am. Chem. Soc. 2005,
127, 5384.
(14) (a) Hamashima, Y.; Sawada, D.; Kanai, M.; Shibasaki, M. J.
Am. Chem. Soc. 1999, 121, 2641. (b) Takamura, M.;
Funabashi, K.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc.
2000, 122, 6327. (c) Shibasaki, M.; Yoshikawa, N. Chem.
Rev. 2002, 102, 2187.
phenyltrimethylsilanyloxyacetonitrile in 74% yield. 1H
NMR (300 MHz, CDCl3): d = 0.08 (s, 9 H), 5.55 (s, 1 H),
7.40–7.60 (m, 5 H). After conversion to acetate, the
enantiomeric excess was determined by HPLC on a
Chiralcel OD column, hexane–i-PrOH, 99:1 (flow rate = 1.0
mL/min), tR (R) 12.92 min (major), tR (S) 14.80 min (minor).
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