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非过渡金属体系促进的 H 活化:LiN(SiMe ) 催化的醛亚胺和酮亚胺的氢化反应。

H Activation by Non-Transition-Metal Systems: Hydrogenation of Aldimines and Ketimines with LiN(SiMe ).

机构信息

Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056, Basel, Switzerland.

Department of Organic Chemistry, Universidad Autónoma de Madrid, c/ Fco. Tomás y Valiente 7, Cantoblanco, 28049, Madrid, Spain.

出版信息

Chemistry. 2019 Feb 6;25(8):1918-1922. doi: 10.1002/chem.201805549. Epub 2019 Jan 11.

Abstract

In recent years, H activation at non-transition-metal centers has met with increasing attention. Here, a system in which H is activated and transferred to aldimines and ketimines using substoichiometric amounts of lithium bis(trimethylsilyl)amide is reported. Notably, the reaction tolerates the presence of acidic protons in the α-position. Mechanistic investigations indicated that the reaction proceeds via a lithium hydride intermediate as the actual reductant.

摘要

近年来,非过渡金属中心的 H 活化受到了越来越多的关注。在这里,我们报道了一种使用亚化学计量的双(三甲基硅基)酰胺锂来活化和转移 H 到醛亚胺和酮亚胺的体系。值得注意的是,该反应能够容忍α-位上酸性质子的存在。机理研究表明,反应通过氢化锂中间体作为实际还原剂进行。

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