Copper-Catalyzed Defluorinative Borylation and Silylation of <i>gem</i>-Difluoroallyl Groups
Trevor W. Butcher, Jonathan Lee Yang, John F. Hartwig
Abstract
Stereodefined (Z)-fluoroalkenes are bioisosteres of amides and synthetic precursors to value-added fluorinated compounds, but their stereoselective synthesis remains challenging. Herein, we report a copper-catalyzed formal SN2′ defluorinative borylation of 3-substituted 3,3-difluoropropenes to form 3-fluoroallylboronic esters in high yields with excellent Z/E ratios. The primary 3-fluoroallylboronic esters undergo several synthetic sequences involving SE2′ substitutions, SN2′ substitutions, and sigmatropic rearrangements to provide tertiary allylic fluorides.
Topics & Concepts
BorylationChemistrySilylationCatalysisCopperOrganic chemistryMedicinal chemistryArylAlkylFluorine in Organic ChemistryOrganoboron and organosilicon chemistryInorganic Fluorides and Related Compounds