金属配合物/手性磷酸参与的不对称接力催化反应

Asymmetric Relay Catalysis Reaction Consisting of Metal Complex and Chiral Phosphoric Acids

金属配合物和有机小分子双体系联合催化的不对称接力催化反应是一新兴热点研究领域.接力催化可以由易得的起始原料生成结构复杂的化合物,实现单一催化剂无法实现的新反应,并且避免了对不稳定中间体的分离纯化,提高了反应的步骤经济性和原子经济性.手性磷酸是近年来研究最为热门的有机小分子催化剂之一,其与金属催化剂结合催化也得到了深入的研究.本工作即针对金属催化剂和手性磷酸结合的接力催化反应的研究进展,做一简要评述.

Metal complex and organo combined catalysis is a new and exciting research area and has attracted close atten- tion. Relay catalysis （or sequential catalysis）, in which both the organocatalyst and the metal catalyst perform two distinct catalytic cycles for the consecutive reactions, enables the assembling readily available starting materials into structurally complex molecules. Besides, relay catalysis can also accomplish unprecedented reactions, which are not accessible through the use of either of the catalytic systems alone. More essentially, it avoids the purification of unstable intermediate and im- proves process economy and atom economy. Chiral phosphoric acids become the hottest kind of organocatalysts in recent decades. Chiral phosphoric acid has been applied to asymmetric transfer hydrogenation of imines, enantioselective Friedel-Craiis reaction, Mannich reaction, hydrophosphonylation reaction, Strecker reaction, aza-Diels-Alder reaction, alky- lation of diazoester reaction and so on. Chiral phosphoric acid can act as both proton donor and proton acceptor simultane- ously, and the system of which combining with metal has attracted intensive study. Transition metal catalysis was dominated in catalytic organic synthesis. Owing to the explosive development of organocatalysis in recent years, the combination of transition metal catalysts and organocatalysts has displayed as a new and powerful strategy for developing new and useful reactions, and has attracted increasing attention. In this review, we summarize recent progress in the field of metal com- plex/phosphoric acids relay catalysis. And in our opinion, the study of new catalysis systems will continue to be an exciting research area, the inquiry of the applications in the total synthesis of natural products is worthy of further investigation and the exploration of appropriate catalysis systems applied in industrial production represents the future research direction.