The Enantioselective Dakin–West Reaction. Issue 8 (25th January 2016)

• Record Type: Journal Article
• Authors: Wende, Raffael C.; Seitz, Alexander; Niedek, Dominik; Schuler, Sören M. M.; Hofmann, Christine; Becker, Jonathan; Schreiner, Peter R.
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 8(2016)
• Page Start: 2719
• Page End: 2723
• Publication Date: 2016-01-25
• Subjects: amino acids -- noncovalent interactions -- organocatalysis -- peptides -- protonation; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201509863
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Here we report the development of the first enantioselective Dakin–West reaction, yielding α‐acetamido methylketones with up to 58 % ee with good yields. Two of the obtained products were recrystallized once to achieve up to 84 % ee . The employed methylimidazole‐containing oligopeptides catalyze both the acetylation of the azlactone intermediate and the terminal enantioselective decarboxylative protonation. We propose a dispersion‐controlled reaction path that determines the asymmetric reprotonation of the intermediate enolate after the decarboxylation. Abstract : Nearly 90 years after its development the first enantioselective Dakin–West reaction is reported. The reaction produces valuable enantioenriched acetamido ketones. The key step is a dispersion‐controlled enantioselective decarboxylative protonation by the catalyst. DCC= N, N ′‐dicyclohexylcarbodiimide.