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钯催化的 N-硝酰氧基羰基苯甲酰胺的分子间邻位 C-H 酰胺化反应。

Pd-catalyzed intermolecular ortho-C-H amidation of anilides by N-nosyloxycarbamate.

机构信息

State Key Laboratory for Chirosciences and The Institute of Molecular Technology for Drug Discovery and Synthesis, Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong.

出版信息

J Am Chem Soc. 2010 Sep 22;132(37):12862-4. doi: 10.1021/ja106364r.

DOI:10.1021/ja106364r
PMID:20735142
Abstract

A palladium-catalyzed ortho-C-H amidation of anilides by N-nosyloxycarbamates was developed for the synthesis of 2-aminoanilines. This reaction can be carried out under relatively mild conditions and exhibits excellent regioselectivity and functional group tolerance. The amidation reaction is probably initiated by rate-limiting C-H cyclopalladation (k(H)/k(D) = 3.7) to form an arylpalladium complex, followed by nitrene functionalization.

摘要

钯催化的 N-硝酰氧基氨基甲酸酯对酰苯胺的邻位 C-H 酰胺化反应被开发用于合成 2-氨基苯胺。该反应可以在相对温和的条件下进行,并表现出优异的区域选择性和官能团耐受性。酰胺化反应可能是通过限速的 C-H 环钯化(k(H)/k(D) = 3.7)引发的,形成芳基钯配合物,然后进行氮宾官能化。

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