Regiodivergent Halogenation of (E)-beta-Chlorovinyl Ketones via Soft alpha-Vinyl Enolization Strategy

Abstract

The soft a-vinyl enolization of (E)-beta-chlorovinyl ketones was investigated in the presence of various halogen electrophiles. Depending on the nature of halogen electrophiles, the selective formation of three products, namely alpha,alpha-dichloropropargyl ketones, alpha,gamma-dihaloallenyl ketones, and 3-halofurans, was observed. The observed regiodivergent nucleophilic pathways of (E)-beta-chlorovinyl ketones demonstrate the diversity-oriented synthesis strategy in which the nucleophilic reactivity of (E)-beta-chlorovinyl ketones can be selectively modulated by the choice of suitable hard and soft electrophiles.