N-Alkylation by Hydrogen Autotransfer Reactions

Review
First Online:
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Accepted:
Part of the following topical collections:
  1. Hydrogen Transfer Reactions

Abstract

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.

Keywords

Alcohols Alcohol activation Alcohol oxidation Amines Amine oxidation Amides N-Alkylation Asymmetric N-alkylation Reductive N-alkylation Dehydration Hydrogen autotransfer Borrowing hydrogen Relay race Transfer hydrogenation Anaerobic dehydrogenation Aerobic oxidative dehydrogenation Homogeneous catalysis Heterogeneous catalysis Transition metal catalysts Transition metal-free Catalyst-free Autocatalysis 
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Notes

Acknowledgments

We thank ZJNSF for Distinguished Young Scholars (LR14B020002), NNSFC (51502174), 580 Overseas Talents Program of Wenzhou, and Science and Technology Project of Shenzhen (JCYJ20150324141711616) for financial support.

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Copyright information

© Springer International Publishing Switzerland 2016

Authors and Affiliations

  1. 1.College of Chemistry and Materials EngineeringWenzhou UniversityWenzhouChina
  2. 2.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 EngineeringShenzhen UniversityShenzhenChina

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