Recent Advance in the C−F Bond Functionalization of Trifluoromethyl Aromatic and Carbonyl Compounds

Abstract The selective C−F bonds functionalization in available trifluoromethyl compounds is an economic route for obtaining high‐value organic fluorine compounds. However, due to the high C−F bonds dissociation energy in trifluoromethyl group, the strength of the bond decreases continuously during defluorination, posing a challenge in modifying such molecules without over‐conversion. Over the past few years, there has been significant progress in developing efficient methods for constructing difluoromethylene unit, using approaches such as radical chemistry, photochemistry, electrochemistry, and organometallic chemistry. These methods involve difluorocarbon radicals, difluorocarbon cations, difluorocarbon anions, and trifluoromethyl carbenes as intermediates. In this review, we summarized the recent five years of research achievements in this field for selective single C−F bond cleavage in trifluoromethyl aromatic and carbonyl compounds to gain diverse difluoromethylene‐containing organic molecules via different intermediate strategies.