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羧酸盐配体对钯催化的分子内C(sp³)-H和C(sp²)-H芳基化反应的空间效应

Steric Effect of Carboxylate Ligands on Pd-Catalyzed Intramolecular C(sp )-H and C(sp )-H Arylation Reactions.

作者信息

Tanji Yutaka, Mitsutake Naoya, Fujihara Tetsuaki, Tsuji Yasushi

机构信息

Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Kyoto, 615-8510, Japan.

出版信息

Angew Chem Int Ed Engl. 2018 Aug 6;57(32):10314-10317. doi: 10.1002/anie.201804566. Epub 2018 Jun 19.

Abstract

A bulky carboxylic acid bearing three cyclohexylmethyl substituents at the α-position, namely, tri(cyclohexylmethyl)acetic acid, is demonstrated to act as an efficient ligand source in Pd-catalyzed intramolecular C(sp )-H and C(sp )-H arylation reactions. The reactions proceed smoothly under mild reaction conditions, even at room temperature due to the steric bulk of the carboxylate ligands, which accelerates the rate-determining C-H bond activation step in the catalytic cycle.

摘要

一种在α位带有三个环己基甲基取代基的庞大羧酸,即三(环己基甲基)乙酸,被证明在钯催化的分子内C(sp³)-H和C(sp²)-H芳基化反应中作为一种有效的配体来源。由于羧酸根配体的空间位阻,反应在温和的反应条件下,甚至在室温下也能顺利进行,这加速了催化循环中决定反应速率的C-H键活化步骤。

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