College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang, 325035, China.
SZU-NUS Collaborative Innovation Center for Optoelectronic Science and Technology, Key Laboratory of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province, College of Optoelectronic Engineering, Shenzhen University, Shenzhen, 518060, China.
Top Curr Chem (Cham). 2016 Jun;374(3):27. doi: 10.1007/s41061-016-0027-1. Epub 2016 Apr 29.
Owing to the importance of amine/amide derivatives in all fields of chemistry, and also the green and environmentally benign features of using alcohols as alkylating reagents, the relatively high atom economic dehydrative N-alkylation reactions of amines/amides with alcohols through hydrogen autotransfer processes have received much attention and have developed rapidly in recent decades. Various efficient homogeneous and heterogeneous transition metal catalysts, nano materials, electrochemical methods, biomimetic methods, asymmetric N-alkylation reactions, aerobic oxidative methods, and even certain transition metal-free, catalyst-free, or autocatalyzed methods, have also been developed in recent years. With a brief introduction to the background and developments in this area of research, this chapter focuses mainly on recent progress and technical and conceptual advances contributing to the development of this research in the last decade. In addition to mainstream research on homogeneous and heterogeneous transition metal-catalyzed reactions, possible mechanistic routes for hydrogen transfer and alcohol activation, which are key processes in N-alkylation reactions but seldom discussed in the past, the recent reports on computational mechanistic studies of the N-alkylation reactions, and the newly emerged N-alkylation methods based on novel alcohol activation protocols such as air-promoted reactions and transition metal-free methods, are also reviewed in this chapter. Problems and bottlenecks that remained to be solved in the field, and promising new research that deserves greater future attention and effort, are also reviewed and discussed.
由于胺/酰胺衍生物在化学各个领域的重要性，以及使用醇作为烷基化试剂的绿色和环境友好的特点，通过氢自动转移过程，醇的相对高原子经济性的胺/酰胺的脱水 N-烷基化反应近年来受到了极大关注，并迅速发展。近年来，还开发了各种高效的均相和多相过渡金属催化剂、纳米材料、电化学方法、仿生方法、不对称 N-烷基化反应、需氧氧化方法，甚至某些无过渡金属、无催化剂或自催化方法。本章简要介绍了该研究领域的背景和发展情况，主要侧重于过去十年中推动该研究发展的最新进展和技术及概念上的进步。除了对均相和多相过渡金属催化反应的主流研究外，还对 N-烷基化反应中关键的氢转移和醇活化的可能机理途径进行了综述，这些途径在过去很少讨论，但最近关于 N-烷基化反应的计算机理研究的报道，以及基于新型醇活化方案（如空气促进反应和无过渡金属方法）的新出现的 N-烷基化方法，也在本章中进行了综述。还对该领域仍待解决的问题和瓶颈以及值得未来更大关注和努力的有前景的新研究进行了综述和讨论。
