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

Abstract

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 enantioselective total synthesis of (-)-aspewentins A, B, and C is demonstrated.

• Authors: Yiyang Liu, Scott C Virgil, Robert H Grubbs, Brian M Stoltz
• Journal: Angewandte Chemie (International ed. in English) (Angew Chem Int Ed Engl) Vol. 54 Issue 40 Pg. 11800-3 (Sep 28 2015) ISSN: 1521-3773 [Electronic] Germany
• PMID: 26230413 (Publication Type: Journal Article)
• Copyright: © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.