钯催化末端炔烃羰基化研究进展

Research Progress in Palladium-Catalyzed Carbonylation of Terminal Alkynes

炔烃羰基化生成α,β-不饱和羰基化合物是许多基础有机合成的重要中间体,在药物合成、农用化学品、香料等方面有巨大的应用价值。有效利用C1资源使钯催化的羰基化反应既具原子经济性又具高选择性。最早得到α,β-不饱和羰基化合物的钯催化体系多为强酸、金属盐等作为助剂的均相钯盐体系,随后几十年,科研工作者们利用固体有机酸以减少该反应对环境的污染和设备的腐蚀,还开发了新型配体体系,大幅度提高了该反应的转化率和选择性。均相体系不易分离、纯化繁琐等缺点限制了其应用。近年来,均相催化多相化研究再次成为热点,将钯催化剂负载在多孔固体表面,不仅可以提高催化剂的比表面积,使其拥有更多的活性位点,还可解决产物与催化剂难分离等问题。本文综述了钯催化末端炔烃羰基化的相关报道,介绍了均相体系中溶剂、助剂和配体对炔烃催化羰基化产物的影响,同时也介绍了非均相钯催化炔烃羰基化反应的研究进展,展望了钯催化末端炔烃羰基化反应发展的趋势和方向。

The carbonylation of alkyne to formα,β-unsaturated carbonyl compounds is an important intermediate for many basic organic synthesis,which has great application value in drug synthesis,agricultural chemicals,spices and so on.The effective utilization of C1 resources makes the palladium-catalyzed carbonylation have atom economy and high selectivity.The first palladium catalyst system to obtainα,β-unsatura-ted carbonyl compounds was a homogeneous palladium salt system with strong acids,metal salts as cocatalysts.In the following decades,researchers used solid organic acid to reduce its pollution to the environment and equipment,then developed new ligand systems to improve the conversion and selectivity of the reaction.Homogeneous system is not easy to be separated and purification,which limits its application.In recent years,people′s focus has been on heterogeneous catalysis.Loading palladium catalyst on porous solid surface can not only increase specific surface area and have more active sites,but also solve the problem of difficult separation of product and catalyst.In this review,we mainly describe the related reports of palladium catalyzed carbonylation of terminal alkynes.The effects of solvents,promoters and ligands in homogeneous system on the products of alkyne catalyzed carbonylation are introduced.At the same time,the research progress of heterogeneous palladium catalyzed carbonylation of alkynes is also summarized.The development trend and direction of palladium catalyzed carbonylation of terminal alkynes are prospected.