Orthogonal Relay Catalysis Enabling Diastereodivergent One‐Pot Syntheses: Access to Enders‐Type Products and Syn/Anti ‐selective Michael/Mannich Adducts

We report two enantio‐ and diastereodivergent transformations based on a one‐pot relay catalysis strategy. Chiral cyclohexenecarbaldehydes, diastereomeric to the products of Enders’ seminal triple domino reaction, were synthesized with excellent enantioselectivity using two structurally related chiral catalysts in a sequential fashion. While the anti ‐isomer was obtained via a one‐pot Michael/Mannich reaction catalyzed by a single chiral catalyst, the complementary syn ‐isomer was selectively accessed through sequential addition of two distinct catalysts in a single vessel. In most cases optically pure products were obtained. This one‐pot relay catalysis strategy enables access to complementary stereoisomers and represents a valuable alternative to traditional domino reactions and single‐catalyst one‐pot processes involving independent catalytic cycles.