Enantioselective Heck Arylations of Acyclic Alkenyl Alcohols Using a Redox-Relay Strategy

作者: E. W. Werner , T.-S. Mei , A. J. Burckle , M. S. Sigman

DOI: 10.1126/SCIENCE.1229208

关键词: SelectivityKetoneChain walkingOrganic chemistryMigratory insertionEnantioselective synthesisRegioselectivityCatalysisChemistryAlkene

摘要: Progress in the development of asymmetric Heck couplings arenes and acyclic olefins has been limited by a tenuous understanding factors that dictate selectivity migratory insertion β-hydride elimination. On basis key mechanistic insight recently garnered exploration selective reactions, we report here an enantioselective variant delivers β-, γ-, or δ-aryl carbonyl products from alkenol substrates. The catalyst system imparts notable regioselectivity during promotes migration alkene’s unsaturation toward alcohol to ultimately form ketone product. reaction uses aryldiazonium salts as arene source, yields enantiomeric opposite starting alkene configurations, readily accessible ligand. racemic nature substrate does not bias enantioselection.

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