Palladium-Catalyzed Asymmetric Direct Intermolecular Allylation of α-Aryl Cyclic Vinylogous Esters: Divergent Synthesis of (+)-Oxomaritidine and (−)-Mesembrine
Wei Wang, Jun Dai, Qiqiong Yang, Yu‐Hua Deng, Fangzhi Peng, Zhihui Shao
Abstract
We demonstrate that α-aryl cyclic vinylogous esters are competent substrates in the direct intermolecular Pd-catalyzed asymmetric allylic alkylation, enabling a straightforward enantioselective synthesis of 6-allyl-6-aryl-3-ethoxycyclohex-2-en-1-ones, common motifs embedded in numerous structurally diverse natural products. As an initial demonstration of the utility of this protocol, the first catalytic enantioselective total synthesis of (+)-oxomaritidine and an improved five-step catalytic enantioselective synthesis of (-)-mesembrine have been completed divergently.
Topics & Concepts
Enantioselective synthesisChemistryTsuji–Trost reactionCatalysisArylPalladiumIntermolecular forceAllylic rearrangementCombinatorial chemistryOrganic chemistryStereochemistryMoleculeAlkylChemical synthesis and alkaloidsAlkaloids: synthesis and pharmacologyAsymmetric Synthesis and Catalysis