Abstract

AbstractThis study demonstrates the feasibility and inherent benefits of combining two distinct asymmetric transition‐metal‐catalyzed reactions in one pot. The reported transformation features a Pd‐catalyzed asymmetric allylic alkylation and a Rh‐catalyzed enantioselective 1,4‐conjugate addition, effectively converting simple allyl enol carbonate precursors into enantioenriched cyclic ketones with two remote stereocenters. Despite the anticipated challenges associated with controlling stereoselectivity in such a complex system, the products are obtained in enantiomeric excesses ranging up to >99 % ee, exceeding those obtained from either of the individual asymmetric reactions. In addition, since the stereoselectivity of both steps is under catalyst control, this one‐pot reaction is enantio‐ and diastereodivergent, enabling facile access to all stereoisomers from the same set of starting materials.

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