Readily Accessible, Modular, and Tuneable BINOL 3,3‘-Perfluoroalkylsulfones: Highly Efficient Catalysts for Enantioselective In-Mediated Imine Allylation

Thia−Fries rearrangement of BINOL perfluoroalkylsulfonates affords readily derivatized novel mono- and disulfone ligands in just two steps from enantiomerically pure BINOL. These electron-demanding BINOLs have been successfully applied as catalysts for indium-mediated allylation of N -acylhydrazones. A general and highly enantioselective catalytic process is described, in which the presence of two perfluoroalkylsulfone (SO 2 R F ) groups is shown to be crucial for activity and selectivity. The allylation process affords the corresponding homoallylic amines up to 99% yield and 99% ee.