钯和手性磷酸协同催化高效构建手性分子的研究进展

Recent Advances of Efficient Synthesis of Chiral Molecules Promoted by Pd/Chiral Phosphoric Acid Synergistic Catalysis

过渡金属钯催化不对称反应是高效合成手性化合物的重要途径之一,在过去几十年里,发展迅速并取得了巨大的进展,但有些反应仅使用钯催化体系难以获得高的反应活性和优异的立体选择性.将过渡金属钯催化体系和有机小分子催化体系联合起来有利于解决单一催化剂面临的难点问题,是合成化学的研究热点之一,备受人们的青睐.近些年,运用过渡金属钯和手性磷酸的协同催化体系,高效地实现了一系列不对称催化反应,良好地控制了化学选择性、区域选择性和立体选择性,已经取得了一些可观的研究成果和重要的突破.简要综述了运用该协同催化体系实现不对称烯丙基化反应、C(sp^(3))—H键官能团化反应、C(sp^(2))—H键官能团化反应以及一些其它类型不对称催化反应的研究现状,系统地分析了催化剂与底物之间的相互作用机制,深入地讨论了影响反应活性和选择性的因素.

Transition metal palladium-catalyzed asymmetric reaction is an important and efficient method to synthesize chiral compounds.It has made considerable progress and achieved great success in the past decades.However,some reactions could not achieve high reactivity and excellent stereoselectivity just promoted by transition metal palladium catalysis.Therefore,it is of great significance to combine transition metal palladium catalysis and organocatalysis,which could be conducive to dissolve these challenging problems and received great attention.In recent years,a variety of asymmetric catalytic reactions have been efficiently realized by the synergistic catalysis system of transition metal palladium catalysis and chiral phosphoric acids with high chemo-,regio-,and stereoselectivity,and considerable research results and some important breakthroughs have been achieved.The recent progress of asymmetric allylation reaction,C(sp^(3))—H,C(sp^(2))—H functionalization and other reactions promoted by this synergistic catalysis system is summarized,the interaction between catalysts and substrates is systematically analyzed,and the influence factors of reactivity and selectivity are deeply discussed.