Stereoselective Rhodium(I)-Catalyzed C-F Bond Arylation of Tri-and Tetrasubstituted gem-Difluoroalkenes with Boronic Acids

We herein describe a highly diastereoselective rhodium(I)-catalyzed C-F bond functionalization of gem-difluoroalkenes with arylboronic acids. In contrast to previously developed Pd(II)- and Pd(0)-catalyzed methods, the Rh(I)/BINAP catalytic system enabled the C-F bond arylation of both trisubstituted beta,beta-difluorostyrenes and tetrasubstituted beta,beta-difluoroacrylates in >99:1 dr toward the synthesis of valuable monofluoroalkenes. Experimental and computational studies suggested a plausible migratory insertion/beta-F elimination mechanism with the [Rh(I)-Ar] species.

Automated summary

In this paper, a highly diastereoselective rhodium(I)-catalyzed C-F bond functionalization of gem-difluoroalkenes with arylboronic acids is described. Unlike previously developed methods using Pd(II) and Pd(0) catalysts, the Rh(I)/BINAP catalytic system enables the C-F bond arylation of both trisubstituted beta,beta-difluorostyrene and tetrasubstituted beta,beta-difluoroacrylate, resulting in the synthesis of valuable monofluoroalkenes with a >99:1 diastereomeric ratio.