Methods to prepare vicinal amino alcohols are important because of their presence in biologically active compounds. Despite the development of various methods for vicinal amino alcohol synthesis, C(sp3)-rich oxygen-containing β-amine compounds continue to pose great challenge. While ring-opening reaction of epoxides with amine nucleophile is the prime method for vicinal amino alcohol preparation, epoxides are highly reactive and sometimes difficult to make, resulting in drawbacks regarding selectivity of this approach. Here, we report a catalytic enantio-convergent amination of α-tertiary 1,2-diols for the efficient access to vicinal amino α-tertiary alcohols. The racemic α-tertiary 1,2-diol substrates of different alkyl/aryl or alkyl/alkyl backbone, can be converted to chiral vicinal amino α-tertiary alcohols through diphenyl phosphate-mediated RuCl