Issue 48, 2023

A general approach to stereospecific Pd-catalyzed cross-coupling reactions of benzylic stereocenters

Abstract

We have developed a general process for the formation of enantioenriched benzylic stereocenters via stereospecific Pd-catalyzed cross-coupling reactions of enantioenriched benzylic tricyclohexyltin nucleophiles. This process proceeds with excellent stereospecificity for a remarkably broad scope of electrophilic coupling partners including aryl and heteroaryl halides and triflates, acid chlorides, thioesters, chloroformates, and carbamoyl chlorides. Thus, enantioenriched 1,1-diarylalkanes as well as formal products of asymmetric enolate arylation are readily accessed using this approach. We additionally provide the first demonstration of a Sn-selective cross-coupling reaction using a vicinal alkylborylstannane nucleophile. In these reactions, the presence of cyclohexyl spectator ligands on tin is essential to ensure selective transfer of the secondary benzylic unit from tin to palladium.

Graphical abstract: A general approach to stereospecific Pd-catalyzed cross-coupling reactions of benzylic stereocenters

Supplementary files

Article information

Article type
Edge Article
Submitted
26 Aug 2023
Accepted
15 Nov 2023
First published
24 Nov 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2023,14, 14124-14130

A general approach to stereospecific Pd-catalyzed cross-coupling reactions of benzylic stereocenters

M. Binayeva, X. Ma, P. Ghaemimohammadi and M. R. Biscoe, Chem. Sci., 2023, 14, 14124 DOI: 10.1039/D3SC04519F

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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