Palladium-catalyzed coupling of tetraorganotin compounds with aryl and benzyl halides. Synthetic utility and mechanism

David Milstein, J. K. Stille

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407 Citations (Scopus)

Abstract

Palladium complexes catalyze the coupling of tetraorganotin compounds with benzyl and aryl halides, benzylchlorobis(triphenylphosphine)palladium(II) (1) being the catalyst of choice. Various functional groups are tolerated by this reaction and generally high yields of the cross-coupled products are obtained. Oxygen has a considerable accelerating effect on the reaction, whereas triphenylphosphine has little effect. The reaction of substituted bromobenzenes with tetramethyltin catalyzed by 1 is accelerated by electron-withdrawing groups; however, a simple Hammett correlation is not observed. Optically active α-deuteriobenzyl bromide reacts with tetramethyltin to afford optically active α-deuterioethylbenzene with inversion of configuration. Homocoupling is the main reaction observed when lithium or Grignard reagents react with benzyl chloride under the influence of various palladium catalysts.

Original languageEnglish
Pages (from-to)4992-4998
Number of pages7
JournalJournal of the American Chemical Society
Volume101
Issue number17
Publication statusPublished - 1979

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Palladium
Bromobenzenes
Benzyl Compounds
Catalysts
Bromides
Lithium
Functional groups
Electrons
Oxygen
triphenylphosphine

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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AU - Stille, J. K.

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AB - Palladium complexes catalyze the coupling of tetraorganotin compounds with benzyl and aryl halides, benzylchlorobis(triphenylphosphine)palladium(II) (1) being the catalyst of choice. Various functional groups are tolerated by this reaction and generally high yields of the cross-coupled products are obtained. Oxygen has a considerable accelerating effect on the reaction, whereas triphenylphosphine has little effect. The reaction of substituted bromobenzenes with tetramethyltin catalyzed by 1 is accelerated by electron-withdrawing groups; however, a simple Hammett correlation is not observed. Optically active α-deuteriobenzyl bromide reacts with tetramethyltin to afford optically active α-deuterioethylbenzene with inversion of configuration. Homocoupling is the main reaction observed when lithium or Grignard reagents react with benzyl chloride under the influence of various palladium catalysts.

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