A highly enantioselective addition of diphenylphosphite to ketimines derived from isatins has been developed employing bifunctional thiourea-tertiary amine organocatalysts. A variety of isatins derived ketimines react well with diphenylphosphite in the presence of Cinchona-derived thiourea (epiCDT) to provide biologically important chiral 3-substituted 3-amino-2-oxindoles (3a–l) in good yield (up