Litcius/Paper detail

Stereodivergent Construction of Csp<sup>3</sup>−Csp<sup>3</sup>Bonds Bearing Vicinal Stereocenters by Synergistic Palladium and Phase‐Transfer Catalysis

Jingqiang Han, Rixin Liu, Zitong Lin, Weiwei Zi

2022Angewandte Chemie International Edition59 citationsDOI

Abstract

Abstract Synergistic catalysis has emerged as one of the most powerful tools for stereodivergent formation of Csp 3 −Csp 3 bonds bearing vicinal stereocenters. Despite the many successes that have been achieved in this field, stereodivergent Csp 3 −Csp 3 coupling reactions involving stabilized nucleophiles remain challenging because of the competing single‐catalysis pathway. Herein, we report a synergistic palladium/phase‐transfer catalyst system that enables diastereodivergent Csp 3 −Csp 3 coupling reactions of 1,3‐dienes with stabilized nucleophile oxindoles. Both the syn and anti coupling products, bearing quaternary and tertiary vicinal stereocenters, could be selectively produced in good yields with high enantio‐ and diastereoselectivities. Non‐covalent activation of the stabilized nucleophile via chiral ion pair in a biphasic system is a crucial success factor in achieving diastereodivergence.

Topics & Concepts

StereocenterVicinalNucleophileChemistryCatalysisPalladiumCombinatorial chemistryEnantioselective synthesisStereochemistryOrganic chemistryAsymmetric Synthesis and CatalysisAsymmetric Hydrogenation and CatalysisCatalytic C–H Functionalization Methods