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钯催化烯醇醚与亚胺和醇的双官能化反应合成氨基缩醛。

Palladium-catalyzed difunctionalization of enol ethers to amino acetals with aminals and alcohols.

机构信息

State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences , Lanzhou 730000, People's Republic of China.

出版信息

J Am Chem Soc. 2013 Dec 11;135(49):18327-30. doi: 10.1021/ja410611b. Epub 2013 Nov 23.

Abstract

A new strategy was developed for intercepting the palladium-alkyl species generated in Heck reaction via nucleophilic addition prior to the step of migratory insertion, which leads to a new palladium-catalyzed difunctionalization of enol ethers with aminals and alcohols to afford amino acetals. Mechanistic studies suggested that the cationic cyclometalated Pd(II) complex generated by the oxidative addition of aminal to a Pd(0) species was crucial for this unusual transformation.

摘要

开发了一种新策略,用于在 Heck 反应中钯-烷基物种发生迁移插入步骤之前通过亲核加成来拦截它们,从而导致烯醚与亚胺和醇的新型钯催化双官能化反应,生成氨基缩醛。机理研究表明,亚胺的氧化加成到 Pd(0)物种生成的阳离子环金属化 Pd(II)配合物对于这种不寻常的转化至关重要。

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