Electron-Transfer-Mediated Synthesis of Phenanthridines by Intramolecular Arylation of Anions from N-(o-Halobenzyl)arylamines. Regiochemical and Mechanistic Analysis

BUDÉN, M. E.; DORN, V. B.; GAMBA, M.; PIERINI, A. B.; ROSSI, R. A.

AMER CHEMICAL SOC

Año: 2010 vol. 75 p. 2206 - 2206

he synthesis of a series of substituted phenanthridines by photostimulated C-C cyclization of anions from N-(ortho-halobenzyl)arylamines is informed to proceed in very good to excellent yields (79-95%) in liquid ammonia and in DMSO as solvents. The N-(ortho-halobenzyl)arylamines are obtained in good to very good isolated yields (44-85%) by nucleophilic substitution of ortho-halobenzylchlorides with different arylamines. The reaction of the anions of a diverse set of N-(ortho-halobenzyl)arylamines was studied and the methodology was extended to the synthesis of trispheridine, a natural product, in very good yield. In order to explain the regiochemical outcome of these reactions a theoretical analysis was performed with DFT methods and the B3LYP functional.