Palladium(II)-Catalyzed Directed anti-Hydrochlorination of Unactivated Alkynes with HCl

A regio­selective anti-hydrochlorination of unactivated alkynes is reported. The reaction utilizes in situ generated HCl as the source of both the Cl– and H+ and is catalyzed by palladium­(II) acetate, with loadings as low as 25 ppm. Removable picolinamide and 8-aminoquinoline bidentate directing groups are used to control the regio­selectivity of the chloropalladation step and stabilize the resulting alkenylpalladium­(II) intermediate for subsequent protodepalladation. This method provides access to a broad array of substituted alkenyl chlorides in excellent yields and with high regio­selectivity. The products from this transformation were successfully derivatized via Stille coupling to a variety of trisubstituted alkene products. Reaction progress kinetic analysis was performed, shedding light on a possible mechanism for this catalytic process.