Synthesis of 2,2-Disubstituted 2H-Chromenes through Carbon-Carbon Bond Formation Utilizing a [1,2]-Phospha-Brook Rearrangement under Brønsted Base Catalysis.

Abstract

A new methodology for the synthesis of 2,2-disubstituted 2H-chromenes was developed by utilizing the [1,2]-phospha-Brook rearrangement under Brønsted base catalysis. Phosphazene P2-tBu efficiently catalyzed the addition reaction of 4H-chromen-4-ols containing a diethoxyphosphoryl group with α,β-unsaturated ketones, which involved the catalytic generation of a carbanion through the [1,2]-phospha-Brook rearrangement and subsequent conjugate addition at the 2-position to afford adducts possessing an alkenylphosphate moiety in a highly diastereoselective manner. Further transformation of the adducts based on a nickel-catalyzed cross-coupling reaction with arylzinc reagents provided densely functionalized 2,2-disubstituted 2H-chromenes.