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Nickel-Catalyzed Atroposelective Cross-Electrophile Coupling of Aryl Halides: A General and Practical Route to Diverse MOP-Type Ligands

Raphael S. Kim, Lebogang O. Kgoadi, Jacob C. Hayes, Derek Rainboth, Catherine M. Mudd, Glenn P. A. Yap, Donald A. Watson

2024Journal of the American Chemical Society26 citationsDOIOpen Access PDF

Abstract

We report a highly cross- and atroposelective coupling between ortho -(chloro)arylphosphine oxides and ortho -(bromo)aryl ethers. This previously unknown asymmetric nickel-catalyzed reaction offers a direct route to highly enantioenriched axially chiral biaryl monophosphine oxides that are difficult to access by other means. These products can be readily reduced to generate chiral MOP-type ligands bearing complex skeletal backbones. The utility of these chiral ligands in asymmetric catalysis is also demonstrated.

Topics & Concepts

ChemistryElectrophileArylNickelHalideCatalysisCombinatorial chemistryCoupling (piping)Medicinal chemistryOrganic chemistryAlkylEngineeringMechanical engineeringAxial and Atropisomeric Chirality SynthesisMolecular spectroscopy and chiralityAsymmetric Synthesis and Catalysis
Nickel-Catalyzed Atroposelective Cross-Electrophile Coupling of Aryl Halides: A General and Practical Route to Diverse MOP-Type Ligands | Litcius