铜催化对C-C不饱和键铜氢化引发的多米诺反应

Domino Reactions Initialized by Copper-Catalyzed Hydrocupration of C-C Unsaturated Bonds

总结了由铜催化的对C-C不饱和键铜氢化反应引发的多米诺反应,反应过程包括铜氢活性物种的产生、对C-C不饱和键的加成及铜氢物种的再生,其中的C-C不饱和键来源于α,β-不饱和酮、α,β-不饱和羧酸酯、芳基烯烃、脂族族烯烃以及炔烃.反应中氢硅烷作为氢负离子源,铜氢化反应产生的中间体随后对极性不饱和键如羰基和亚胺进行加成反应或对饱和键进行取代反应,最终生成两个或多个化学键.反应不需要对中间产物进行纯化,也不需要改变操作条件,方法简洁高效,在有机合成中有重要的应用价值.

Compared with sequential reactions, domino reactions are more efficient and highly desirable in organic synthesis as fewer operational and purification procedures are involved, yielding the product with complexity in a more economic and environmently friendly manner. Domino reactions induced by copper-catalyzed hydrocupration of unsaturated C-C bonds inα,β-unsaturated ketones, α,β-unsaturated carboxylates, aryl alkenes, aliphatic alkenes and even alkynes are reviewed. A hydrosilane is used as a hydride source for Cu H formation and the hydrocupration intermediates undergo subsequent addition to polar unsaturated bonds, e.g. carbonyls and imines, or proceed to substitution reactions, and finally, reaction involving two or more newly formed bonds proceed without purification of intermediate products or changing the operational conditions.Because of its simplicity and efficiency, this method is highly valuable in organic synthesis.