Abstract An efficient and general protocol for the palladium-catalyzed Heck alkynylation of benzyl chlorides was developed. A catalyst system comprised of PdCl 2 (CH 3 CN) 2 and 2- dicyclohexylphosphino-2′, 4′, 6′-triisopropylbiphenyl (XPhos), with Cs 2 CO 3 as the base, efficiently couples a wide range of functionalized terminal alkynes and substituted benzyl chlorides at 65 C. We have also demonstrated that the corresponding aryl allene ...