Experimental and Computational Studies of the Iron-Catalyzed Selective and Controllable Defluorosilylation of Unactivated Aliphatic gem-Difluoroalkenes

Abstract

The first iron-catalyzed defluorosilylation of unactivated gem-difluoroalkenes was developed, delivering gem-disilylated alkenes and (E)-silylated alkenes with excellent efficiency. This protocol features good functional group compatibility and excellent regio- and stereoselectivity, enabling the late-stage silylation of biologically relevant compounds, thus providing good opportunities for applications in medicinal chemistry. Preliminary mechanistic studies and DFT calculations reveal that a nucleophilic addition and elimination of the second C-F bond might be involved in the disilylation catalytic system, demonstrating unusual reactivity characteristics of iron catalysis.

Keywords: C−F bond cleavage; gem-disilylated alkenes; high selectivity; iron catalysis.