1.9 Trifluoromethoxylation and Other Fluoroalkoxylation Reactions

Abstract In this review, methods to achieve the direct fluoroalkoxylation of a variety of substrates are dis-cussed, including transformations of arenes/hetarenes and compounds with carbon–carbon multiple bonds, and reactions at C(sp3) carbon centers. These reactions involve the introduction of fluoroalkoxy groups, including CF3O, CHF2O, and (CF3)2CFO, into organic molecules. Several types of methodology are discussed for achieving these transformations, including thermal radical processes, electron-transfer mechanisms, photocatalysis, electrochemical approaches, and redox-neutral radical pathways. The methods employ either radical fluoroalkoxylating reagents or nucleophilic fluoroalkoxylating sources of the fluorinated group.