Enantio‐ and Diastereoselective Synthesis of Chiral Allenes by Palladium‐Catalyzed Asymmetric [3+2] Cycloaddition Reactions. Issue 39 (5th September 2018)

• Record Type: Journal Article
• Authors: Trost, Barry M.; Zell, Daniel; Hohn, Christoph; Mata, Guillaume; Maruniak, Autumn
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 39(2018)
• Page Start: 12916
• Page End: 12920
• Publication Date: 2018-09-05
• Subjects: [3+2] cycloaddition -- asymmetric catalysis -- chiral allenes -- DYKAT -- reaction mechanism; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201808345
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A protocol for the asymmetric synthesis of highly substituted chiral allenes with control of point and axial chirality has been developed. A palladium‐catalyzed [3+2] cycloaddition using readily available racemic allenes gives access to densely functionalized chiral allenes with excellent yields and functional group tolerance. The catalytic asymmetric protocol utilizes a broad range of allenyl TMM (trimethylenemethane) donors to form cyclopentanes, pyrrolidines, and spirocycles with very good control of regio‐, enantio‐, and diastereoselectivity. The chiral allene moiety is shown to be a valuable functional group for rapid elaboration towards complex targets. Abstract : A palladium‐catalyzed [3+2] cycloaddition of racemic allenes to form densely functionalized chiral allenes has been developed. This catalytic asymmetric procedure was utilized to obtain various cyclopentanes, pyrrolidines, and spirocycles with very good control over the regio‐, enantio‐, and diastereoselectivity.