On the stereochemical course of palladium-catalyzed cross-coupling of allylic silanolate salts with aromatic bromides

Scott E. Denmark, Nathan S. Werner

Research output: Contribution to journalArticle

Abstract

The stereochemical course of palladium-catalyzed cross-coupling reactions of an enantioenriched, a-substituted, allylic silanolate salt with aromatic bromides has been investigated. The allylic silanolate salt was prepared in high geometrical (Z/E, 94:6) and high enantiomeric (94:6 er) purity by a coppercatalyzed SN2′ reaction of a resolved allylic carbamate. Eight different aromatic bromides underwent crosscoupling with excellent constitutional site-selectivity and excellent stereospecificity. Stereochemical correlation established that the transmetalation event proceeds through a syn SE′ mechanism which is interpreted in terms of an intramolecular delivery of the arylpalladium electrophile through a key intermediate that contains a discrete Si-O-Pd linkage.

Original languageEnglish (US)
Pages (from-to)3612-3620
Number of pages9
JournalJournal of the American Chemical Society
Volume132
Issue number10
DOIs
StatePublished - Mar 17 2010

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ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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