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.