Is oxidative addition indeed the rate-determining step of the Suzuki-Miyaura reaction with less-reactive aryl chlorides under "ligand-free" conditions?

被引：10

作者：

Schmidt, Alexander F. ^{[1
]}

Kurokhtina, Anna A. ^{[1
]}

Larina, Elizaveta V. ^{[1
]}

Vidyaeva, Elena V. ^{[1
]}

Lagoda, Nadezhda A. ^{[1
]}

机构：

[1] Irkutsk State Univ, Dept Chem, 1 K Marx St, Irkutsk 664003, Russia

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2020年 / 929卷

基金：

俄罗斯科学基金会;

关键词：

Suzuki-Miyaura reaction; Aryl chlorides; Palladium; Mechanism; Kinetics; COUPLING REACTIONS; REDUCTIVE ELIMINATION; HECK REACTIONS; BROMIDES; IODIDES; HALIDES;

D O I：

10.1016/j.jorganchem.2020.121571

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The retarded oxidative addition of aryl chloride to Pd(0) is believed, by most scientists, to be the main hindrance in achieving effective conversion in the Suzuki-Miyaura reaction and other cross-coupling reac-tions of aryl chlorides. Herein, we have demonstrated by competing experiments, using two aryl chlorides under "ligand-free" catalytic conditions (absence of strong ligands; high ratio of substrate to catalyst), that the elementary step of oxidative addition is substantially reversible. This implies that the hypothesis on the rate-determining character of the oxidative addition step is incorrect, and the existing problems with aryl chloride conversion in the Suzuki-Miyaura reaction are caused by some other reasons that need to be investigated. (C) 2020 Elsevier B.V. All rights reserved.

引用

页数：5

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