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苯氧钠-氧化膦作为用于与酮进行 Mukaiyama 羟醛缩合反应的极具活性的路易斯碱催化剂。

Sodium phenoxide-phosphine oxides as extremely active Lewis base catalysts for the Mukaiyama aldol reaction with ketones.

作者信息

Hatano Manabu, Takagi Eri, Ishihara Kazuaki

机构信息

Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa, Nagoya, 464-8603, Japan.

出版信息

Org Lett. 2007 Oct 25;9(22):4527-30. doi: 10.1021/ol702052r. Epub 2007 Sep 26.

Abstract

A highly efficient Mukaiyama aldol reaction between ketones and trimethylsilyl enolates catalyzed by sodium phenoxide-phosphine oxides as simple homogeneous Lewis base catalysts (0.5-10 mol %) was developed, which minimized competing retro-aldol reaction. For a variety of aromatic ketones and aldimines, aldol and Mannich-type products with an alpha-quaternary carbon center were obtained in good to excellent yields. Up to 100 mmol scale of benzophenone and trimethylsilyl enolate with 0.5 mol % of catalyst was established in 97% yield (34.8 g).

摘要

开发了一种由苯氧基钠-氧化膦作为简单均相路易斯碱催化剂(0.5-10 mol%)催化的酮与三甲基硅烯醇化物之间的高效Mukaiyama羟醛缩合反应,该反应将竞争性的逆羟醛缩合反应降至最低。对于各种芳香酮和醛亚胺,以良好至优异的产率获得了具有α-季碳中心的羟醛缩合和曼尼希型产物。使用0.5 mol%的催化剂,在高达100 mmol规模的二苯甲酮和三甲基硅烯醇化物反应中,产率达到97%(34.8 g)。

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