title: Modeling mechanisms of unusual benzene imine n6 adduct formation in carcinogenic reactions of arylnitrenium ions with adenosine.
abstract: Reaction mechanisms of the unusual benzene imine N6 adduct formation in carcinogenic reactions of arylnitrenium ions with adenosine have been investigated with density functional theory (DFT) and high-level ab initio methods. The DFT calculations indicate that the reaction pathways initiated by attack of adenine at the ortho C site of 4-biphenylylnitrenium ion are favored. However, high-level MP2 and QCISD calculations provide a contrary conclusion, that is the reaction pathways initiated by attack of adenine at the para C site of 4-biphenylylnitrenium ion are more feasible. Comparing with experimental results, the conclusion from high-level ab initio calculations is ultimately supported. The present study makes a theoretical prediction on the final products in the studied reaction, which is in agreement with experimental observations. In addition, this study provides some inspirations to the attacks of arylnitrenium ions at amino group of purines and pyrimidines in similar carcinogenic reactions.
authors.affiliation: Chemistry and Chemical Engineering Faculty, Liaoning Normal University, Dalian 116029, People's Republic of China.
authors.forename: Shi-Fei
authors.initials: SF
authors.lastname: Qi
authors.forename: Zhong-Zhi
authors.initials: ZZ
authors.lastname: Yang
mesh_terms: D000241:Adenosine / Q000737:chemistry*; D000611:Aminobiphenyl Compounds / Q000737:chemistry*; D001554:Benzene / Q000737:chemistry*; D002273:Carcinogens / Q000737:chemistry*; D007097:Imines / Q000737:chemistry*; D007477:Ions / Q000737:chemistry; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D011789:Quantum Theory
chemical_list: D000611:Aminobiphenyl Compounds; D002273:Carcinogens; D007097:Imines; D007477:Ions; C006757:4-biphenylamine; D001554:Benzene; D000241:Adenosine