Iterative double cyclization reaction by S(RN)1 mechanism. A theoretical interpretation of the regiochemical outcome of diazaheterocycles

作者：Peisino Lucas E; Camargo Solorzano Gloria P; Buden Maria E^*; Pierini A B

来源：RSC Advances, 2015, 5(46): 36374-36384.

DOI：10.1039/c5ra04563k

In this report, we present a synthetic and mechanistic study of novel iterative double cyclization intramolecular S(RN)1 reactions from diamides bearing two aryl iodide moieties. This cyclization affords aromatic diazaheterocyclic compounds in good yields. Two synthetic strategies were employed for their preparation: intramolecular S(RN)1 and Homolytic Aromatic Substitution. The mechanism is non-trivial and we propose that radicals are intermediates. The regiochemistry was studied using computational calculations, employing the DFT method and the B3LYP functional. It was found that the distribution of products depends on the cyclization activation energies, proportion of neutral conformers, and the type of the electron transfer reaction.

• 出版日期2015