Direct catalytic asymmetric addition of allyl cyanide to ketones via soft lewis acid/hard brønsted base/hard lewis base catalysis

Ryo Yazaki, Naoya Kumagai, Masakatsu Shibasaki

研究成果: Contribution to journalArticle査読

95 被引用数 (Scopus)

抄録

We report that a hard Lewis base substantially affects the reaction efficiency of direct catalytic asymmetric γ-addition of allyl cyanide (1a) to ketones promoted by a soft Lewis acid/hard Brønsted base catalyst. Mechanistic studies have revealed that Cu/(R,R)-Ph-BPE and Li(OC 6H4-p-OMe) serve as a soft Lewis acid and a hard Brønsted base, respectively, allowing for deprotonative activation of 1a as the rate-determining step. A ternary catalytic system comprising a soft Lewis acid/hard Brønsted base and an additional hard Lewis base, in which the basicity of the hard Brønsted base Li(OC6H4-p-OMe) was enhanced by phosphine oxide (the hard Lewis base) through a hard-hard interaction, outperformed the previously developed binary soft Lewis acid/hard Brønsted base catalytic system, leading to higher yields and enantioselectivities while using one-tenth the catalyst loading and one-fifth the amount of 1a. This second-generation catalyst allows efficient access to highly enantioenriched tertiary alcohols under nearly ideal atom-economical conditions (0.5-1 mol % catalyst loading and a substrate molar ratio of 1:2).

本文言語英語
ページ(範囲)5522-5531
ページ数10
ジャーナルJournal of the American Chemical Society
132
15
DOI
出版ステータス出版済み - 4 21 2010
外部発表はい

All Science Journal Classification (ASJC) codes

  • 触媒
  • 化学 (全般)
  • 生化学
  • コロイド化学および表面化学

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