Catalytic Enantioselective Synthesis of 1,4-(Hetero) Dicarbonyl Compounds through α-Carbonyl Umpolung.

ABSTRACT: The enantioselective synthesis of 1,4-dicarbonyl compounds continues to pose a significant challenge in organic synthesis, and a catalytic process which generates two adjacent stereogenic centers with full stereochemical control is lacking until now. The 1,4-relationship of the functional groups requires an Umpolung strategy as one of the α-carbonyl positions has to be inverted into an electrophilic center to react with a normal enolate. We report herein the highly enantio- and diastereoselective addition of silyl ketene acetals toward electrophilic 1-azaallyl cations to furnish chiral 4-hydrazonoesters, which are masked 1,4-dicarbonyl compounds. The products carrying up to 2 new stereogenic centers were obtained in excellent yields across a broad substrate scope. As precursors to the 1-az

SUBMITTER: Friedmann T 

PROVIDER: S-EPMC11744765 | biostudies-literature | 2025 Jan

REPOSITORIES: biostudies-literature