Chemoselectivity Switch between Enantioselective [2,3]-Wittig Rearrangement and Conia-Ene-Type Reactions of Propargyloxyoxindoles

Despite the existence of three competing reactions for propargyloxyoxindoles, we report a chemoselectivity switch between enantioselective propargyl [2,3]-Wittig rearrangement and Conia-ene-type reactions, with suppression of the [1,2]-Wittig-type rearrangement. Using C₁-symmetric imidazolidine-pyrroloimidazolone pyridine as the ligand and Ni(acac)₂ as the Lewis acid, diverse 3-hydroxy 3-substituted oxindoles containing allenyl groups were obtained in up to 98 % yield and 99 % ee via asymmetric propargyl [2,3]-Wittig rearrangement. In the presence of AgOTf-Duanphos, chiral spiro dihydrofuran oxindoles were given in up to 98 % yield and 91 % ee through a Conia-ene-type reaction.