Asymmetric Synthesis of β-Ketoamides by Sulfonium Rearrangement.

Authors :: Porte V
Nascimento VR
Sirvent A
Tiefenbrunner I
Feng M
Kaiser D
Maulide N
Source :: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Dec 16; Vol. 63 (51), pp. e202418070. Date of Electronic Publication: 2024 Nov 16.
Publication Year :: 2024
Abstract: The synthesis of enantioenriched α-substituted 1,3-dicarbonyls remains a contemporary challenge in synthesis due to their tendency to undergo racemization via keto-enol tautomerization. Herein, we report a method to access enantioenriched β-ketoamides by a chiral sulfinimine-mediated [3,3]-sigmatropic sulfonium rearrangement. The transformation displays good chirality transfer, as well as excellent chemoselectivity and functional group tolerance. Diastereoselective reduction of the ketone moiety, also achievable in one-pot fashion, affords enantioenriched β-hydroxyamides.<br /> (© 2024 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.)