A novel type of donor–acceptor cyclopropane with fluorine as the donor: (3 + 2)-cycloadditions with carbonyls

Abstract

gem-Difluorocyclopropane diester is disclosed as a new type of donor–acceptor cyclopropane, which smoothly participates in (3 + 2)-cycloadditions with various aldehydes and ketones. This work represents the first application of gem-difluorine substituents as an unconventional donor group for activating cyclopropane substrates in catalytic cycloaddition reactions. With this method, a wide variety of densely functionalized gem-difluorotetrahydrofuran skeletons, which are otherwise difficult to prepare, could be readily assembled in high yields under mild reaction conditions. Computational studies show that the cleavage of the C–C bond between the difluorine and diester moieties occurs upon a S_N2-type attack of the carbonyl oxygen.