Catalytic carbonylations of alkynes represent straightforward and atom-economic synthesis of a, beta-unsaturated carbonyl compounds. One of the issues associated with the currently known catalytic systems is insufficient efficiency. In this context, Pd/ligand-catalyzed regioselective and efficient alkoxycarbonylation of terminal alkynes is desirable for the synthesis of alpha,beta-unsaturated esters. Herein, we present the use of a newly designed bifunctional ligand for efficient Pd-catalyzed alkoxycarbonylation of alkynes. Both aliphatic and aromatic alkynes were smoothly transformed to the branched desired products with high selectivity (28 examples, 45-96% yields, 95.0-99.9% selectivity). (C) 2018 Elsevier Inc. All rights reserved.