부산대학교 도서관

New methods for the formation of CN bonds to prepare compounds with wide‐ranging applications in medicinal, materials, and synthetic chemistry are continually evolving. Early methods for CN bond formation required prefunctionalized substrates, such as halides, pseudohalides, and carbonyl compounds. These approaches often resulted in increased step count, decreased atom economy, and limitations in functional group compatibility. To address these shortcomings, the direct functionalization of CH bonds has emerged as an attractive strategy. The ability to achieve direct exchange of a hydrogen atom for a nitrogen in the later stages of a synthesis is an especially powerful tool in a synthetic chemist's toolbox. Approaches to direct amination can be subdivided into those containing open‐shell intermediates, which will be described in this article, and concerted pathways, which will not be covered. Topics that will be discussed include strategies for C(sp3)H amination involving both inter‐ and intramolecular 1,n‐hydrogen atom transfer (HAT), intermolecular C(sp3)H amination, C(sp3)H amination via nitrene transfer, and net C(sp2)H amination. Traditional examples as well as the more recent strategies that utilize photo‐ and electrochemical methods are presented. Selected examples from the literature will be presented, but previous reviews and articles are referenced here for further reading.