Methodologies in Amine Synthesis

Nitrogen radicals are powerful intermediates in synthetic chemistry. Their ability to undergo selective H‐atom transfer reactions represents a valuable tool for the assembly and functionalization of organic molecules. Although the large body of work and examples are already available, several challenges are still unsolved. For example, the ability to control in a general sense the stereochemical outcome of these transformations is currently not possible but would be highly desirable. Furthermore, these processes have rarely been used in large‐scale settings, especially at an industrial level, so further work would be required to identify reaction protocols that can be translated into process development. Finally, an area where continuous development and application is required involves the use of these strategies for the late‐stage modification of complex and bioactive materials. The ability to selectively target specific and unactivated sp 3‐centers, where a functionality can be introduced, would represent a powerful tool in order to better explore chemical space around lead molecules.

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Binbin Huang1, Yating Zhao2, and Wujiong Xia1

1Harbin Institute of Technology, State Key Lab of Urban Water Resource and Environment, School of Science, Shenzhen, 518055, China

2Quzhou University, College of Chemical and Material Engineering, Quzhou, China, 324000

As ubiquitous fundamental linkages, C—N bonds prevalently exist in various value‐added compounds such as natural products, pharmaceutical agents, functional materials, synthetic intermediates, and coordinating ligands. Thus, developing efficient methodologies for the construction of C—N bonds has always been a hot research goal in synthetic chemistry [1]. Among the existing approaches toward C—N bonds, cross‐dehydrohalogenative couplings of C—H/N—X (X = halide or pseudo ‐halide) bonds or C—X/N—H bonds are generally well established, highly efficient, and consequently widely used, including the classical Buchwald–Hartwig amination and Ullman amination. However, from the perspective of green chemistry, these methods are not the ideal choices because the requirement for prefunctionalization of the coupling substrates considerably lowers their atom and step economy.