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.

Phenols are converted into aryl diethyl phosphate esters (ArDEP), which on reaction with sodium trimethylstannide (1) or sodium triphenylstannide (2) in liquid ammonia afford arylstannanes by the S RN 1 mechanism. Thus, the photostimulated reaction of phenylDEP (3), (4-methoxyphenyl)DEP ( 4), (4-biphenyl)DEP ( 5), (1-naphthyl)DEP ( 6), (2-naphthyl)DEP ( 7), and 2-(34), 3-(32), and (4-pyridyl)DEP ( 35) with 1 leads to monostannylated product in fair to excellent yields (20-98%). Also, substrates containing two or three leaving groups react with 1 under irradiation, affording the corresponding di-or tristannylated aryl compounds. With tetraethyl m-phenylene bisphosphate (15), tetraethyl p-phenylene bisphosphate ( 21), (4-chlorophenyl)DEP ( 22), and 1,3,5-tris(diethylphospho)benzene ( 30), the di-or trisubstitution products 1,3-bis(trimethylstannyl)benzene ( 19) (79%), 1,4-bis(trimethylstannyl)benzene ( 23) (95 and 97%), and 1,3,5-tris(trimethylstannyl)benzene (31) (57%) are obtained, respectively. Also, the reaction of 6 and 7 with 2 leads to substitution products in quantitative yields, and the reaction of 21, 22, and (4-bromophenyl)DEP ( 24) with 2 affords 1,4-bis(triphenylstannyl)benzene (38) in high yields (70-100%). On the other hand, the results obtained in the photostimulated reaction of 24 and (4-iodophenyl)DEP ( 25) with 1, as well as in the reaction of 25 with 2, clearly indicate a fast HME reaction.