Catalytic carbonylations of alkynes represent straightforward and atom-economic synthesis of α,β-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 α,β-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).

炔烃的催化羰基化代表了α，β-不饱和羰基化合物的直接且原子经济的合成。与当前已知的催化系统相关的问题之一是效率不足。在这种情况下，末端α炔的Pd /配体催化的区域选择性和有效的烷氧羰基化对于合成α，β-不饱和酯是合乎需要的。在本文中，我们介绍了新设计的双功能配体在炔烃有效Pd催化烷氧基羰基化反应中的应用。脂族和芳族炔烃均能以高选择性顺利转化为支链所需产物（28个实例，产率为45-96％，选择性为95.0-99.9％）。