Transition-metal-catalyzed C(sp3)–H bond fluorination reactions

• Published in: Chem catalysis Vol. 4; no. 7; p. 101009
• Main Authors: Ge, Robbie, Xu, Ziting, Yang, Ke, Ge, Haibo
• Format: Journal Article
• Language: English
• Published: Elsevier Inc 18.07.2024
• Subjects: C(sp3)–H bond; electrochemistry; fluorination; photochemistry; transition metal catalyzed; transition metal catalyzed; fluorination; electrochemistry; photochemistry; C(sp3)–H bond; SDG9: Industry, innovation, and infrastructure
• ISSN: 2667-1093; 2667-1093
• DOI: 10.1016/j.checat.2024.101009

Constructing C−F bonds via C−H activation has been a subject of considerable attention in the field of organic synthesis. Within this reaction class, the popularity of transition-metal-catalyzed approaches has substantially expanded in recent years. Currently, there are two main types of these reaction pathways. The first type involves the formation of a carbon-metal-fluorine intermediate with the assistance of a directing group. The second type utilizes a transition metal species to generate a radical or carbocation intermediate. Despite the importance of these reactions, there has yet to be a comprehensive review of transition-metal-catalyzed C(sp3)−H bond fluorination processes. This review presents major advances in and detailed mechanistic discussions of transition-metal-catalyzed C(sp3)−H bond fluorination reactions with different reaction modes under various thermal, photochemical, and electrochemical conditions. [Display omitted] The selective construction of C–F bonds is a highly active research field in pharmaceutical and agricultural chemistry, as well as materials science. In this field, the utilization of transition-metal-catalyzed C(sp3)–H fluorination has emerged as a prominent and remarkably efficient strategy for synthesizing diverse molecules containing fluorine. Considering their importance in organic chemistry, this review introduces the major advances in the field of transition-metal-catalyzed C(sp3)–H bond fluorination reactions under thermal, photochemical, and electrochemical conditions. Additionally, detailed mechanistic discussions have been provided to help readers gain insights in this area. Ge et al. provide and discuss the historical background and significant advancements in transition-metal-catalyzed C(sp3)–H bond fluorination reactions via different modes of action under thermal, photochemical, and electrochemical conditions. Additionally, they provide comprehensive discussions on reaction mechanisms alongside a forward-looking perspective on innovative strategies within this field.