Electron-Transfer-Mediated Synthesis of Phenanthridines by IntramolecularArylation of Anions fromN-(ortho-Halobenzyl)arylamines: Regiochemical and Mechanistic Analysis

MARÍA E. BUDÉN, VIVIANA B. DORN, MARTINA GAMBA, ADRIANA B. PIERINI, AND ROBERTO A. ROSSI

JOURNAL OF ORGANIC CHEMISTRY

AMER CHEMICAL SOC

Lugar: Washington; Año: 2010 vol. 75 p. 2206 - 2218

0022-3263

The synthesis of a series of substituted phenanthridines by photostimulated C-C cyclization of anions from N-(ortho-halobenzyl)arylamines has been found to proceed in very good to excellent yields (79-95%) in liquid ammonia and in DMSO. The N-(ortho-halobenzyl)arylamines are obtained in good to very good isolated yields (44-85%) by nucleophilic substitution of orthohalobenzylchlorides with different arylamines. The reaction of the anions of a diverse set of N-(orthohalobenzyl) 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.