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Transition metal‐catalyzed cross‐coupling reactions have become a powerful and widely used synthetic approach for the construction of both carbon‐carbon and carbon‐heteroatom bonds. These reactions have revolutionized synthetic chemistry by enabling the efficient formation of complex molecular architectures. Among the various methods available, the bimolecular homolytic substitution (SH2) reaction has emerged as an attractive and versatile method for the formation of C(sp3)−C(sp3) and C(sp3)‐heteroatom bonds. In recent years, significant progress has been made in the development of radical SH2 reactions, particularly those involving different transition metal complexes such as cobalt, nickel, and iron. These advancements have expanded the scope of SH2 reactions, allowing for greater diversity in substrate compatibility and reaction conditions. In this review, we aim to highlight the latest breakthroughs and mechanistic insights into radical SH2 reactions, focusing on the role of transition metal catalysts in facilitating these transformations. We will discuss the various types of transition metal complexes that have been employed, the mechanistic pathways involved, and the potential applications of these reactions in the synthesis of complex organic molecules. [ABSTRACT FROM AUTHOR]

Catalytic multicomponent reactions offer an efficient synthetic approach for constructing multiple chemical bonds in a single step. However, the carboamination of unactivated alkenes, involving nitrogen radical species directly from N–H precursors, is infrequent due to the high bond energy and challenges in step matching. Herein we demonstrate a catalytic radical three-component reaction using simple primary sulfonamides, which provides a novel method for constructing a library of complex architectures through carbon–nitrogen and carbon–carbon bond formation. The newly developed method demonstrates a high degree of tolerance towards various functional groups, proving to be highly efficient in the late-stage modification of complex drug molecules and natural products under very mild conditions. [ABSTRACT FROM AUTHOR]