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Enantioselective Heck arylations of acyclic alkenyl alcohols using a redox-relay strategy.

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

SUBMITTER: Werner EW

PROVIDER: S-EPMC3583361 | biostudies-literature | 2012 Dec

REPOSITORIES: biostudies-literature

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Enantioselective Heck arylations of acyclic alkenyl alcohols using a redox-relay strategy.

Werner Erik W EW Mei Tian-Sheng TS Burckle Alexander J AJ Sigman Matthew S MS

Science (New York, N.Y.) 20121201 6113

Progress in the development of asymmetric Heck couplings of arenes and acyclic olefins has been limited by a tenuous understanding of the factors that dictate selectivity in migratory insertion and β-hydride elimination. On the basis of key mechanistic insight recently garnered in the exploration of selective Heck reactions, we report here an enantioselective variant that delivers β-, γ-, or δ-aryl carbonyl products from acyclic alkenol substrates. The catalyst system imparts notable regioselect ...[more]

PMID: 23239733

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