Stereoselective Construction of Trisubstituted 1,3‐Enynes <i>via</i> 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 6 H 4 OH as additive. Mechanistic investigations suggest that cleavage of the olefinic C−H bond might not be involved in the rate‐determining step of the catalytic process.