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 (SO2RF) 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.