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钯催化的酰胺 C(sp3)-H 位 α-选择性乙酰化反应:一种不寻常的环钯化反应机理。

Pd-catalyzed α-selective C(sp3)-H acetoxylation of amides through an unusual cyclopalladation mechanism.

机构信息

CAS Key Laboratory of Receptor Research, and Synthetic Organic & Medicinal Chemistry Laboratory (SOMCL), Shanghai Institute of Materia Medica (SIMM), Chinese Academy of Sciences, Shanghai 201203, China.

出版信息

Chem Commun (Camb). 2015 Feb 21;51(15):3219-22. doi: 10.1039/c4cc09576f.

Abstract

We report the first example of Pd-catalyzed site-selective α-C(sp(3))-H oxidation/acetoxylation of amides through an unusual [4,6]-bicyclic metallacycle intermediate with 1-aminoanthraquinone as a new bidentate directing group. In addition to the distinct mechanism and high efficiency, the reaction is highly appealing due to the ample commercial source, low-cost, as well as easy removal and recycling of the auxiliary group.

摘要

我们报告了首例钯催化的酰胺的α-C(sp(3))-H 氧化/乙酰化的位点选择性反应,该反应通过一种不寻常的[4,6]-双环金属环中间体和 1-氨基蒽醌作为新的双齿导向基团来实现。除了独特的机制和高效率外,由于辅助基团有充足的商业来源、低成本以及易于去除和回收,该反应具有很大的吸引力。

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