有机小分子和金属联合催化是指用有机小分子和金属等多种催化剂同时或连续活化不同底物、官能团或中间体,从而完成催化反应。该策略可以实现单一催化剂无法完成的反应。根据催化剂活化模式的不同,有机小分子和金属联合催化可以分为协同催化、接力催化与连续催化。近年来,随着有机小分子催化的快速发展以及人们对金属和有机催化的理解越来越深入,有机小分子和金属联合催化方面的报道逐年增加,正在发展成为均相不对称催化中受到广泛关注的新兴研究领域。钯配合物是重要的过渡金属催化剂,钯催化在有机合成中具有十分广泛的应用。本文重点总结了钯和手性有机小分子联合不对称催化方面的进展,主要包括手性胺、手性布朗斯特酸以及手性亲核催化剂等有机催化剂与钯联合催化,同时指出了该领域内一些亟待解决的问题,并对未来的发展作了展望。
Organo/metal combined catalysis integrates the catalytic activity of the organocatalyst and metal complex to enable the creation of unprecedented protocols by simultaneous or sequential activation of chemical bonds. On the basis of the activation modes and catalytic pathways, the combined catalysis could be divided into cooperative catalysis, relay catalysis and sequential catalysis. In recent years, the metal/organo combined catalysis has received a great deal of attention, leading to many unprecedented protocols thanks to increasingly deep insight into the concepts of organocatalysis and transition-metal catalysis. Palladium complexes have been one of the most important types of transition metal catalysts and have widely been applied to the organic synthesis. This review will be focused on highlighting recent progress in asymmetric combined catalysis of chiral organocatalysts and palladium complexes, including chiral amines, Brønsted acids, and nucleophilic Lewis bases combined with palladium complexes for the creation of unprecedented transformations. The key issues that need to be addressed in this field are discussed and the perspective of the emerging area are also described.
Contents
1 Introduction
2 Chiral amine/palladium combined catalysis
3 Chiral Brønsted acid/palladium combined catalysis
4 Chiral nucleophilic Lewis base/palladium combined catalysis
5 Conclusion
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