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Palladium-Catalyzed Decarbonylative Dehydration for the Synthesis of ?-Vinyl Carbonyl Compounds and Total Synthesis of (-)-Aspewentins A, B, and C.

ABSTRACT: The direct ?-vinylation of carbonyl compounds to form a quaternary stereocenter is a challenging transformation. It was discovered that ?-oxocarboxylic acids can serve as masked vinyl compounds and be unveiled by palladium-catalyzed decarbonylative dehydration. The carboxylic acids are readily available through enantioselective acrylate addition or asymmetric allylic alkylation. A variety of ?-vinyl quaternary carbonyl compounds are obtained in good yields, and an application in the first enantioselective total synthesis of (-)-aspewentins A, B, and C is demonstrated.

SUBMITTER: Liu Y

PROVIDER: S-EPMC4686263 | biostudies-literature | 2015 Sep

REPOSITORIES: biostudies-literature

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Palladium-Catalyzed Decarbonylative Dehydration for the Synthesis of α-Vinyl Carbonyl Compounds and Total Synthesis of (-)-Aspewentins A, B, and C.

Liu Yiyang Y Virgil Scott C SC Grubbs Robert H RH Stoltz Brian M BM

Angewandte Chemie (International ed. in English) 20150729 40

The direct α-vinylation of carbonyl compounds to form a quaternary stereocenter is a challenging transformation. It was discovered that δ-oxocarboxylic acids can serve as masked vinyl compounds and be unveiled by palladium-catalyzed decarbonylative dehydration. The carboxylic acids are readily available through enantioselective acrylate addition or asymmetric allylic alkylation. A variety of α-vinyl quaternary carbonyl compounds are obtained in good yields, and an application in the first enanti ...[more]

PMID: 26230413

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