Enantio- and Diastereodivergent Sequential Catalysis featuring Two Transition Metal-Catalyzed Asymmetric Reactions.

Abstract

This 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 starting from the same set of starting materials.