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

Authors :
N. A. Lagoda
Alexander F. Schmidt
Elena V. Vidyaeva
A. A. Kurokhtina
E. V. Larina
Source :
Journal of Organometallic Chemistry. 929:121571
Publication Year :
2020
Publisher :
Elsevier BV, 2020.

Abstract

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 reactions 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.

Details

ISSN :
0022328X
Volume :
929
Database :
OpenAIRE
Journal :
Journal of Organometallic Chemistry
Accession number :
edsair.doi...........9986cc49646c6da23e2c2ab1a4f56a02
Full Text :
https://doi.org/10.1016/j.jorganchem.2020.121571