Palladium-Catalyzed C–H Amination/[2 + 3] or [2 + 4] Cyclization via C(sp<sup>3</sup> or sp<sup>2</sup>)–H Activation
Yang An, Yuke Li, Xiaoyan Zhang, Zhe Zhang, Xue‐Ya Gou, Yanan Ding, Li Qiao, Yong‐Min Liang
Abstract
This report describes a palladium-catalyzed Catellani reaction consisting of amination/[2 + 3] or [2 + 4] cyclization via a carboxylate ligand-exchange strategy. This method effectively activates ortho-substituents that avoid a second C–H palladation. The scope of substrates was broad, o-methyl-substituted iodoarenes were applied to the reaction smoothly, and o-phenyl-substituted iodoarenes can also be obtained by this method. In terms of mechanism, density functional theory calculations proved the sequence of the key five-membered aryl-norbornene-palladacycle intermediate formation and C(sp3 or sp2)–H activation.
Topics & Concepts
ChemistryPalladiumCatalysisAminationCarboxylateNorborneneArylMedicinal chemistryLigand (biochemistry)Density functional theoryStereochemistryOrganic chemistryComputational chemistryMonomerBiochemistryPolymerAlkylReceptorCatalytic C–H Functionalization MethodsSynthesis and Catalytic ReactionsCatalytic Cross-Coupling Reactions