Pd-catalyzed regioselective hydroarylation of alpha-(2-aminoaryl)-alpha,beta-ynones with organoboron derivatives as a tool for the synthesis of quinolines: experimental evidence and quantum-chemical calculations

摘要

The Pd-catalyzed hydroarylation of beta-(2-aminoaryl)-alpha,beta-ynones with organoboron derivatives, leading to 2,4-diarylquinolines in good to excellent yields through sequential cycloamination, has been investigated. The reaction is catalyzed by both Pd(II) and Pd(0) precatalysts, and can be carried out even under neutral conditions. The regiochemical outcome is inverted with respect to the Pd-catalyzed hydroarylation of beta-(2-aminoaryl)-alpha,beta-ynones with aryl iodides. This aspect has been rationalized using quantum-chemical calculations, which show significant differences between the energy barriers of the regioisomeric transition states for the migratory insertion (hydropalladation) step, and are consistent with the charge density of the pi complex that undergoes such insertion. (C) 2008 Elsevier Ltd. All rights reserved.