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Stereoretentive Catalytic [3+2]-Cycloaddition/Rearrangement/Decarboxylation Reactions of Indoles with Non-Racemic Donor–Acceptor Cyclopropanes

Ming Bao, Karlos Lopez, Raj K. Gurung, Hadi D. Arman, Michael P. Doyle

2023ACS Catalysis28 citationsDOI

Abstract

A highly enantioselective synthesis of chiral dihydro-3 H -carbazole-2-carboxylate derivatives is reported via a “one-pot” cyclopentannulation-rearrangement cascade reaction that is sequentially catalyzed by nickel(II) perchlorate hexahydrate and scandium(III) trifluoromethanesulfonate with 3-methylindole and non-racemic donor–acceptor cyclopropanes in high yields and enantioretention under mild reaction conditions. Highly diastereoselective [3+2]-cycloaddition is dependent on 3-methylindole substituents. In addition, a further transformation of these dihydro-3 H -carbazole-2-carboxylates via hydrolysis and decarboxylation under unexpectedly mild reaction conditions provides straightforward access to the decarboxylated compounds in moderate yields with high retention of enantiomeric purity.

Topics & Concepts

ChemistryDecarboxylationCycloadditionEnantioselective synthesisCarbazoleCatalysisMedicinal chemistryCascade reactionTrifluoromethanesulfonateEnantiomeric excessOrganic chemistryCyclopropane Reaction MechanismsAsymmetric Synthesis and CatalysisCatalytic C–H Functionalization Methods
Stereoretentive Catalytic [3+2]-Cycloaddition/Rearrangement/Decarboxylation Reactions of Indoles with Non-Racemic Donor–Acceptor Cyclopropanes | Litcius