The creation of full stereoisomers of an organic compound comprising multiple contiguous stereocenters with simultaneous control over both relative and absolute configurations remains a significant challenge in synthetic chemistry. Using a cooperative catalysis strategy, we established an N-heterocyclic carbene/nickel-catalyzed enantio- and diastereodivergent propargylation reaction to access 3,3'-disubstituted oxindoles, enabling the incorporation of internal alkyne functionality and the introduction of a single quaternary or vicinal quaternary/tertiary stereogenic center. By selecting the appropriate combination of catalyst chirality, all four potential stereoisomers of α-quaternary propargylated oxindoles were synthesized in a predictable and precise way with remarkable yields, diastereoselectivities, and enantioselectivities from identical starting materials. The synthetic utility of this method was demonstrated in the concise asymmetric total synthesis of (-)-debromoflustramine B and (-)-C(β-Me)-debromoflustramine B.