Phosphine‐Catalyzed Difunctionalization of β‐Fluoroalkyl α,β‐Enones: A Direct Approach to β‐Amino α‐Diazo Carbonyl Compounds

Abstract

AbstractAn efficient and practical phosphine‐catalyzed vicinal difunctionalization of β‐fluoroalkyl α,β‐enones with TMSN3 has been developed. Using dppb as the catalyst, the reaction worked efficiently to yield various β‐amino α‐diazocarbonyl compounds in high yields (up to 94 %). This work marks the first efficient construction of α‐diazocarbonyl compounds by phosphine catalysis. Meanwhile, the asymmetric variant induced by the nucleophilic bifunctional phosphine P4 led to various chiral fluoroalkylated β‐amino α‐diazocarbonyl compounds in high yields and enantioselectivity. NMR and ESI‐MS studies support the existence of the key reaction intermediates. In contrast, β‐azide carbonyl compounds would be furnished in good yields from β‐fluoroalkylated β,β‐disubstituted enones.