Читать книгу Methodologies in Amine Synthesis - Группа авторов - Страница 19

Nitrogen‐containing molecules represent a central class of compounds with applications spanning therapeutic agents, agrochemicals, food additives, and materials. Chemical methodologies able to streamline the synthesis and modification of these molecules underpin the development of high‐value products central to the well‐being of our society [1].

Nitrogen radicals are reactive intermediates with powerful applications to the synthesis of nitrogenated molecules [2]. Their reactivity can be used for direct C—N bond formation via exo‐trig cyclization (Scheme 2.1a) and addition to electron‐rich π‐system (Scheme 2.1b) or for remote sp³ carbon functionalization, exploiting their ability to partake in radical transpositions [3, 4]. From this perspective, there are two types of processes that can be used, β‐fission (Scheme 2.1c) and intramolecular 1,5‐H‐atom transfer (1,5‐HAT) (Scheme 2.1d). The former reactivity normally involves radical ring opening of small cyclic systems, while the latter enables the effective functionalization of N‐containing alkyl chains.

This chapter will discuss selected recent advances in the application of nitrogen radicals in the field of 1,5‐HAT. We will arrange the content highlighting the key mechanistic features of the HAT process and will then divide the discussion on the basis of the chemical process used to access the key nitrogen radicals. In each case, we aim to highlight the application of this radical reactivity in the assembly or the late‐stage functionalization of complex and bioactive materials.