Ru-catalyzed asymmetric hydrogenation of α-substituted α,β-unsaturated ketones has been developed for the enantioselective synthesis of chiral α-substituted secondary alcohols with high diastereo- and enantioselectivities (up to >99 : 1 dr, 98% ee). Mechanistic experiments suggest that the reaction proceeds via a Ru-catalyzed asymmetric hydrogenation of the CO bond in concert with a base-promoted allylic alcohol isomerization, and the final stereoselectivities were controlled by a DKR process during the asymmetric hydrogenation of the ketone intermediate.

中文翻译：

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通过氢化/异构化级联，Ru 催化 α,β-不饱和酮的不对称氢化

Ru 催化的 α-取代 α,β-不饱和酮的不对称氢化已被开发用于手性 α-取代仲醇的对映选择性合成，具有高非对映选择性和对映选择性（高达 >99 : 1 dr，98% ee）。机理实验表明，该反应通过Ru催化的CO键不对称氢化与碱促进的烯丙醇异构化进行，并且最终的立体选择性由酮中间体不对称氢化过程中的DKR过程控制。