Nickel-Catalyzed Carbonylative Negishi Cross-Coupling of Unactivated Secondary Alkyl Electrophiles with 1 atm CO Gas
Yetong Zhang, Qihang Cao, Yang Xi, Xianqing Wu, Jingping Qü, Yifeng Chen
Abstract
We describe a nickel-catalyzed carbonylative cross-coupling of unactivated secondary alkyl electrophiles with the organozinc reagent at atmospheric CO gas, thus allowing the expedient construction of unsymmetric dialkyl ketones with broad functional group tolerance. The leverage of a newly developed NN 2 -pincer type ligand enables the chemoselective three-component carbonylation by overcoming the competing Negishi coupling, the undesired β-hydride elimination, and dehalogenation of alkyl iodides side pathways. Both alkyl iodides and alkyl tosylates are compatible in the single electron transfer involved mechanism.
Topics & Concepts
ChemistryNegishi couplingAlkylCarbonylationElectrophileCatalysisMigratory insertionHalogenationCombinatorial chemistryNickelOrganic chemistryCarbon monoxideCatalytic Cross-Coupling ReactionsCatalytic C–H Functionalization MethodsCarbon dioxide utilization in catalysis