Stereoselective Construction of Trisubstituted 1,3‐Enynes via Aryl to Vinyl 1,4‐Palladium Migration

Abstract

Palladium‐catalyzed stereoselective olefinic C–H alkynylation of gem‐diarylsubstituted ethylenes with propargylic alcohols was achieved to access diverse unsymmetrical 1,3‐enynes. The regio‐ and stereoselectivities were established through a 1,4‐palladium migration from aryl to vinyl in the presence of 2‐FC<sub>6</sub>H<sub>4</sub>OH additive. Mechanistic investigations have suggested that cleavage of the olefinic C–H bond might not be involved in the rate‐determining step throughout the catalytic process.