Catalytic, Regioselective Hydrocarbofunctionalization of Unactivated Alkenes Triggered by trans-Acetoxypalladation of Alkynes

Herein we demonstrate a Pd­(II)-catalyzed regioselective hydrocarbofunctionalization of unactivated alkenes. The σ-vinyl-palladium­(II) intermediate generated by the trans-acetoxypalladation of alkynes was added across carbon–carbon double bond to realize an efficient hydroalkenylation protocol. Bidentate auxiliary 8-aminoquinoline controls the regioselectivity of the carbopalladation step and thereby controls the regioselectivity of the hydroalkenylation. Additionally, when alkynes containing a hydroxy group at the three- or four-position were employed, the cascade sequence led to 1,6-dicarbonyl compounds via hydroalkenylation followed by intramolecular acyl migration.