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β‐Trifluoromethyl (CF3) enones were proved to act as good dienophiles in asymmetric normal‐electron‐demand Diels–Alder cycloadditions with 2,4‐dienals under trienamine catalysis with a chiral secondary amine. The sequential reductive amination transformations with benzylamine produced cis‐ and trans‐fused chiral trifluoromethylated octahydroisoquinolines in a diastereodivergent manner by using NaBH(OAc)...
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