Double Ligands Enabled Ruthenium Catalyzed <i>ortho</i>‐C−H Arylation of Dialkyl Biarylphosphines: Straight and Economic Synthesis of Highly Steric and Electron‐Rich Aryl‐Substituted Buchwald‐Type Phosphines
Liang‐Neng Wang, Pan‐Ting Tang, Ming Li, Jiawei Li, Yue‐Jin Liu, Ming‐Hua Zeng
Abstract
Abstract A double‐ligands enabled ruthenium catalyzed C( sp 2 )−H arylation of dialkyl phosphines is described, which provides a straight access to aryl‐substituted dialkyl phosphine ligands. The combination of 1,3‐diketone and amino acid ligands is essential for this transformation. An important six‐membered cycloruthenium intermediate was successfully isolated and characterized by X‐ray diffraction. Mechanistic studies showed that the 1,3‐diketone promoted the process of oxidative addition of cycloruthenium intermediate. Some of modified CyJohnPhos ligands exhibited highly catalytic activity in palladium catalyzed C−N bond formation. magnified image
Topics & Concepts
ChemistryRutheniumPhosphineSteric effectsArylCatalysisOxidative additionLigand (biochemistry)PalladiumMedicinal chemistryDouble bondStereochemistryCombinatorial chemistryOrganic chemistryReceptorAlkylBiochemistryCatalytic C–H Functionalization MethodsCatalytic Cross-Coupling ReactionsAsymmetric Hydrogenation and Catalysis