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无碱条件下烯醇化羰基化合物与硅烷的脱氢偶联反应。

Base-free dehydrogenative coupling of enolizable carbonyl compounds with silanes.

机构信息

Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 115, 10623 Berlin, Germany.

出版信息

Org Lett. 2012 Jun 1;14(11):2842-5. doi: 10.1021/ol301089r. Epub 2012 May 23.

Abstract

A dehydrogenative coupling between enolizable carbonyl compounds and equimolar amounts of triorganosilanes catalyzed by a tethered ruthenium complex with a Ru-S bond is reported. The complex is assumed to fulfill a dual role by activating the Si-H bond to release a silicon electrophile and by abstracting an α-proton from the intermediate silylcarboxonium ion, only liberating dihydrogen as the sole byproduct. Reaction rates are exceedingly high at room temperature with very low loadings of the ruthenium catalyst.

摘要

一种具有 Ru-S 键的桥连钌配合物催化的烯醇化羰基化合物与等摩尔量的三有机硅烷之间的脱氢偶联反应被报道。该配合物通过活化 Si-H 键释放硅亲电试剂并从中间体硅基羧翁离子中提取α-质子,仅释放氢气作为唯一的副产物,从而被假定起到双重作用。在室温下,反应速率非常高,钌催化剂的负载量非常低。

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