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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.

SUBMITTER: Binayeva M

PROVIDER: S-EPMC10717501 | biostudies-literature | 2023 Dec

REPOSITORIES: biostudies-literature

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

Binayeva Meruyert M Ma Xinghua X Ghaemimohammadi Pejman P Biscoe Mark R MR

Chemical science 20231124 48

We have developed a general process for the formation of enantioenriched benzylic stereocenters <i>via</i> 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 ...[more]

PMID: 38098708

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