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However, the construction of tetrasubstituted heteroatomic <jats:italic>gem<\/jats:italic>\u2010difluoroalkenes by this strategy is still an unsolved problem. Here, we report the first direct X\u2212H bond <jats:italic>gem<\/jats:italic>\u2010difluoroalkenylation of amines and alcohols with trifluoromethyl ketone <jats:italic>N<\/jats:italic>\u2010triftosylhydrazones under silver (for (hetero)aryl hydrazones) or rhodium (for alkyl hydrazones), thereby providing a most powerful method for the synthesis of tetrasubstituted heteroatomic <jats:italic>gem<\/jats:italic>\u2010difluoroalkenes. This method features a broad substrate scope, high product yield, excellent functional group tolerance, and operational simplicity (open air conditions). Moreover, the site\u2010specific replacement of the carbonyl group with a <jats:italic>gem<\/jats:italic>\u2010difluorovinyl ether bioisostere in drug Trimebutine and the post\u2010modification of bioactive\u2009molecules demonstrates potential use in medicinal research. Finally, the reaction mechanism was investigated by combining experiments and DFT calculations, and disclosed that the key step of HF elimination occurred via five\u2010membered ring transition state, and the difference in the electrophilicity of Ag\u2010 and Rh\u2010carbenes as well as the multiple intermolecular interactions rendered the effectiveness of Rh catalyst selectively for alkyl hydrazones.<\/jats:p>","DOI":"10.1002\/chem.202200280","type":"journal-article","created":{"date-parts":[[2022,2,22]],"date-time":"2022-02-22T06:05:36Z","timestamp":1645509936000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":21,"title":["Direct <i>gem<\/i>\u2010Difluoroalkenylation of X\u2212H Bonds with Trifluoromethyl Ketone <i>N<\/i>\u2010Triftosylhydrazones for Synthesis of Tetrasubstituted Heteroatomic 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