Synthetic Advantages of Defluorinative C−F Bond Functionalization

Much progress has been made in the development of methods to both create compounds that contain C-F bonds and to functionalize C-F bonds. As such, C-F bonds are becoming common and versatile synthetic functional handles. This review summarizes the advantages of defluorinative functionalization reactions for small molecule synthesis. The coverage is organized by the type of carbon framework the fluorine is attached to for mono- and polyfluorinated motifs. The main challenges, opportunities and advances of defluorinative functionalization are discussed for each class of organofluorine. Most of the text focuses on case studies that illustrate how defluorofunctionalization can improve routes to synthetic targets or how the properties of C-F bonds enable unique mechanisms and reactions. The broader goal is to showcase the opportunities for incorporating and exploiting C-F bonds in the design of synthetic routes, improvement of specific reactions and advent of new methods.