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Palladium-Catalyzed Regio-, Enantio-, and Diastereoselective Asymmetric [3 + 2] Cycloaddition Reactions: Synthesis of Chiral Cyclopentyl Phosphonates

Barry M. Trost, Anand H. Shinde, Youliang Wang, Zhijun Zuo, Chang Min

2020ACS Catalysis45 citationsDOI

Abstract

The palladium-catalyzed unified approach using in situ-generated Phospha-TMM species to synthesize a diverse array of chiral organophosphorus containing carbo- and heterocyclic compounds in a highly regio-, diastereo- (>20:1 dr), and enantioselective (>99% ee) fashion is being disclosed. The present protocol reveals the potential of the deprotonative phospha-TMM strategy for the synthesis of challenging five-membered carbo- and heterocycles, especially those with spirocyclic entities and quaternary asymmetric stereocenters. The choice of the robust chiral diamidophosphite ligand proved to be very crucial for the desired reactivity in the present transformation. Furthermore, the synthetic utility of the products is demonstrated by multiple transformations such as reductions, oxidations, and alkylations.

Topics & Concepts

StereocenterEnantioselective synthesisPalladiumCycloadditionChemistryCatalysisCombinatorial chemistryReactivity (psychology)StereochemistryLigand (biochemistry)Organic chemistryReceptorAlternative medicineBiochemistryPathologyMedicineAsymmetric Hydrogenation and CatalysisCatalytic C–H Functionalization MethodsChemical Synthesis and Analysis
Palladium-Catalyzed Regio-, Enantio-, and Diastereoselective Asymmetric [3 + 2] Cycloaddition Reactions: Synthesis of Chiral Cyclopentyl Phosphonates | Litcius