Orthogonal Relay Catalysis Enabling Diastereodivergent One‐Pot Syntheses: Access to Enders‐Type Products and <i>Syn/Anti</i> ‐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.