The first iron-catalyzed defluorosilylation of unactivated gem-difluoroalkenes was developed, delivering gemdisilylated alkenes and (E)-silylated alkenes with excellent efficiency.T his protocol features good functional group compatibility and excellent regio-and stereoselectivity,e nabling the late-stage silylation of biologically relevant compounds,t hus providing good opportunities for applications in medicinal chemistry.Preliminary mechanistic studies and DFT calculations reveal that anucleophilic addition and elimination of the second C À Fb ond might be involved in the disilylation catalytic system, demonstrating unusual reactivity characteristics of iron catalysis.Scheme 1. The methods for the synthesis of gem-disilylated alkenes.

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