Highly Selective C-F Bond Functionalization of Tetrasubstituted gem-Difluoroalkenes and Trisubstituted Monofluoroalkenes Using Grignard Reagents

We herein describe selective C-F bond functionalizations of tetrasubstituted gem-difluoroalkenes and trisubstituted monofluoroalkenes using Grignard reagents without the transition metal catalyst. beta,beta-Difluoroacrylates react with Grignard reagents under mild conditions to afford tetrasubstituted (E)-beta-monofluoroacrylates. Experimental and computational studies revealed that the selectivity stems from the intrinsic reactivity difference between the (E)- and (Z)-isomers toward excess Grignard reagent, which leads to the resolution of the two products.

Automated summary

We describe a method for the selective C-F bond functionalization of tetrasubstituted gem-difluoroalkenes and trisubstituted monofluoroalkenes using Grignard reagents without the transition metal catalyst.