Enantioselective Synthesis of Tertiary α,α-Diaryl Carbonyl Compounds Using Chiral N,N'-Dioxides under Umpolung Conditions

Abstract

Brønsted acid-catalyzed addition of the chiral N,N′-dioxide into ynamides generated enolonium ions in situ which underwent enantioselective alkylation by indoles, pyrroles, and phenols, without racemization of the formed tertiary center. This external oxidant approach allows for the use of unmodified nucleophiles and does not leave trace groups from the oxidant, which significantly increases the synthetic efficiency and the product diversity. Furthermore, the byproduct of the N,N′-dioxide could be efficiently recycled into an optically pure form.