ルイス酸-ルイス塩基複合多点認識概念を基盤とした新規不斉触媒反応の開発と展開

概要

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The design, synthesis, and application of a new bifunctional enantioselective catalyst containing both Lewis acidity and Lewis basicity are described. Recent developments of chiral quaternary stereocenter synthesis through catalytic enantioselective Reissert-type reaction and cyanosilylation of ketones forming the S-enantiomer are chiefly reviewed. The catalysts are composed of a lewis acid metal(aluminum, titanium, or lanthanide) and a Lewis base(the oxygen atom of a phosphine oxide), of which positions are defined by 2, 2'-binaphthol(BINOL) or a carbohydrate scaffold. Utilizing these catalysts, we have developed a variety of enantioselective cyanation reactions, such as cyanosilylation of aldehydes and ketones, Strecker-type reaction, and Reissert-type reaction. These reactions showed a broad substrate generality. Investigations toward the elucidation of the reaction mechanism, involving kinetic studies, comparison of the results by control catalysts, and absolute configurations of the products, revealed that these reactions are catalyzed by a dual activation of a substrate and trimethylsilyl cyanide(TMSCN) by the Lewis acid and the Lewis base of these catalysts. Catalytic enantioselective synthesis of several drug lead compounds, such as anti-cancer epothilones, potent N-methyl-D-aspartate(NMDA) receptor antagonists, phenytoin analogs, salsolinol carboxylic acid, and anti-cancer camptothecin was achieved, using these reactios as key steps.
公益社団法人日本薬学会の論文
2001-12-01

著者

金井求
東京大学大学院薬学系研究科

ルイス酸-ルイス塩基複合多点認識概念を基盤とした新規不斉触媒反応の開発と展開

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