Synlett 2006(11): 1762-1764  
DOI: 10.1055/s-2006-944201
LETTER
© Georg Thieme Verlag Stuttgart · New York

Enantioselective Dialkylzinc Addition to Aldehydes Catalyzed by Chiral Zn(II)-BINOLates Bearing Phosphonates and Phosphoramides in the 3,3′-Positions

Manabu Hatano, Takashi Miyamoto, Kazuaki Ishihara*
Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa, Nagoya 464-8603, Japan
Fax: +81(52)7893222; e-Mail: ishihara@cc.nagoya-u.ac.jp;
Further Information

Publication History

Received 10 April 2006
Publication Date:
04 July 2006 (online)

Abstract

Highly enantioselective dialkylzinc addition to a series of aldehydes was developed based on chiral Zn(II)-BINOLate catalysts bearing phosphonates [P(=O)(OR)2] and phosphoramides [P(=O)(NMe2)2] at the 3,3′-positions. The reactions proceeded smoothly and showed reductions in the amounts of both catalysts and dialkylzinc reagents to be loaded.

    References and Notes

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10

For hexanal in entry 13, 3 mol% of (R)-3 with 1.5 equiv of Et2Zn was more reactive than 10 mol% of 3,3′-bis(diphenylphosphinoyl)-BINOL (71%) with 3 equiv of Et2Zn in our previous report. See ref. 7.

11

Ligands 1-3 were stable under air and moisture conditions. We could easily recover these ligands from the reaction mixture by silica gel column chromatography.