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Bifunctional Iminophosphorane Superbases Enable the Highly Enantioselective Sulfa-Michael Addition to Fully Substituted Cyclopropene Carboxylic Acid Derivatives

Kang Yuan, Alberto I. Ristache, Szymon M. Kosc, Agamemnon E. Crumpton, Darren J. Dixon

2025Journal of the American Chemical Society7 citationsDOIOpen Access PDF

Abstract

High Resolution Image Download MS PowerPoint Slide The metal-free catalytic enantioselective intermolecular conjugate addition of alkyl thiols to unactivated β-substituted cyclopropene carboxylic acid derivatives has been developed. High enantiomeric excesses and yields were consistently achieved across a broad range of thiol pronucleophiles and fully substituted cyclopropene electrophiles under mild reaction conditions, enabled by a novel tert -leucine-derived amide-containing bifunctional iminophosphorane (BIMP) catalyst. Additionally, lowering the catalyst loading to 5.0 mol % was possible and allowed the reaction to be carried out on a gram scale.

Topics & Concepts

ChemistryCyclopropeneBifunctionalEnantioselective synthesisElectrophileCarboxylic acidCatalysisOrganic chemistryAlkylEnantiomerAddition reactionOrganocatalysisConjugateIntermolecular forceReactivity (psychology)Medicinal chemistryBifunctional catalystCombinatorial chemistryCyclopropane Reaction MechanismsSynthetic Organic Chemistry MethodsSynthesis and Catalytic Reactions
Bifunctional Iminophosphorane Superbases Enable the Highly Enantioselective Sulfa-Michael Addition to Fully Substituted Cyclopropene Carboxylic Acid Derivatives | Litcius