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Ramachary et al. “A Brønsted Acid-Primary Amine as a Synergistic-catalyst for Stereoselective Asymmetric. Herein, we present the Brønsted-acid-controlled, primary-amine-catalyzed stereoselective asymmetric synthesis of druglike six-membered spirooxindoles from simple aliphatic substrates through a Barbas [4+2]-cycloaddition reaction by using 2-aminobuta-1,3-diene catalysis under ambient conditions.