C−F Bond Insertion: An Emerging Strategy for Constructing Fluorinated Molecules

Abstract

C‐F Insertion reactions, where an organic fragment formally inserts into a carbon‐fluorine bond in a substrate, are highly attractive, yet largely unexplored, methods to prepare valuable fluorinated molecules. The inherent strength of C‐F bonds and the resulting need for a large thermodynamic driving force to initiate C‐F cleavage often leads to sequestering of the released fluoride in an unreactive by‐product. Recently, however, several groups have succeeded in overcoming this challenge, opening up the study of C‐F insertion as an efficient and highly atom‐economical approach to prepare fluorinated compounds. In this article, the recent breakthroughs are discussed focusing on the key conceptual advances that allowed for both C‐F bond cleavage and subsequent incorporation of the released fluoride into the product.