Electron-transfer-mediated synthesis of phenanthridines by intramolecular arylation of anions from N-(ortho-halobenzyl)arylamines: regiochemical and mechanistic analysis.
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 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.
Budén
María E
ME
INFIQC, Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, Argentina.
Dorn
Viviana B
VB
Gamba
Martina
M
Pierini
Adriana B
AB
Rossi
Roberto A
RA
D000588:Amines / Q000737:chemistry*; D000641:Ammonia / Q000737:chemistry; D000838:Anions / Q000737:chemistry*; D001596:Benzylamines / Q000737:chemistry*; D020650:Combinatorial Chemistry Techniques; D003500:Cyclization; D006846:Hydrocarbons, Halogenated / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D010617:Phenanthridines / Q000138:chemical synthesis* / Q000737:chemistry; D012996:Solutions / Q000737:chemistry
D000588:Amines; D000838:Anions; D001596:Benzylamines; D006846:Hydrocarbons, Halogenated; D010617:Phenanthridines; D012996:Solutions; D000641:Ammonia