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A direct asymmetric substitution was developed for the reaction of cyclic Morita–Baylis–Hillman alcohols with 3‐benzyl‐2‐oxindoles that are catalyzed by a primary amine derived from alkaloids in combination with trifluoroacetic acid. The unusual δ‐products with vicinal chiral quaternary and tertiary carbon centers were obtained as the major products in yields up to 73 % with excellent diastereoselectivities...
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