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Asymmetric Synthesis of N‐Fused 1,3‐Oxazolidines via Pd‐Catalyzed Decarboxylative (3+2) Cycloaddition

Jong‐Un Park, Hye‐In Ahn, Ho‐Jun Cho, Zi Xuan, Ju Hyun Kim

2020Advanced Synthesis & Catalysis38 citationsDOI

Abstract

Abstract Efficient synthesis of optically active N‐fused 1,3‐oxazolidines containing quaternary and tertiary stereocenters was achieved via Pd‐catalyzed asymmetric (3+2) cycloadditions of sulfamate‐derived cyclic imines and vinylethylene carbonates. Using a chiral phosphoramidite ligand, the cycloadditions proceeded effectively providing sulfamidate‐fused 1,3‐oxazolidines in high yields (up to 96%) with stereoselectivities (up to 25:1 dr; >99% ee). Additionally, the scale‐up reaction and further transformations of the product were also achieved demonstrating the synthetic utility toward the construction of useful heterocycles such as chiral oxazoline bearing a quaternary stereocenter. magnified image

Topics & Concepts

StereocenterChemistryPhosphoramiditeCycloadditionOxazolineCatalysisEnantioselective synthesisOptically activeLigand (biochemistry)Combinatorial chemistryStereochemistryOrganic chemistryReceptorDNAOligonucleotideBiochemistrySynthesis and Catalytic ReactionsAsymmetric Hydrogenation and CatalysisCatalytic C–H Functionalization Methods