Synthesis of α-Trifluoromethylamines by Cu-Catalyzed Regio- and Enantioselective Hydroamination of 1-Trifluoromethylalkenes

A copper-catalyzed regioselective net hydroamination of 1-trifluoromethylalkenes with hydrosilanes and hydroxylamines has been developed. The judicious choice of ligand and additive suppresses the conceivable but undesired β-F elimination of an α-CF3-substituted organocopper intermediate, leading to targeted α-trifluoromethylamines in good yields with excellent regioselectivity. Additionally, with an appropriate chiral bisphosphine ligand, the enantioselective reaction is also possible to deliver optically active α-trifluoromethylamines of high potential in medicinal and pharmaceutical chemistry.Takata T., Hirano K., Miura M.. Synthesis of α-Trifluoromethylamines by Cu-Catalyzed Regio- and Enantioselective Hydroamination of 1-Trifluoromethylalkenes. Organic Letters. 21(11), 4284-4288, (2019),7 June 2019; © 2019 American Chemical Society. https://doi.org/10.102/acs.orglett.9b01471

Synthesis of gem-difluoroalkenes by copper-catalyzed regioselective hydrodefluorination of 1-trifluoromethylalkenes

A copper-catalyzed regioselective hydrodefluorination of 1-trifluoromethylalkenes with hydrosilanes has been developed. The copper catalysis is compatible with several functional groups, including alkyl chloride, ether, ester, nitrile, and imide moieties, to form the corresponding gem-difluoroalkenes in good yields. Additionally, asymmetric induction is also possible by using the chiral DTBM-SEGPHOS ligand, and gem-difluoroalkene with point chirality at the allylic position is obtained with high enantioselectivity