title: Computational studies on the reactivity of substituted 1,2-dihydro-1,2-azaborines.
abstract: We have investigated important intermediates of electrophilic aromatic substitution reactions and one-electron oxidation of substituted 1,2-dihydro-1,2-azaborines with density-functional theory. The results show that electrophilic substitution reactions and one-electron oxidation of substituted 1,2-azaborines are generally much more favorable than those of the corresponding benzene derivatives. Both chlorination and nitration of several boron-unsubstituted 1,2-azaborines are expected to break the boron-hydrogen bond, yielding boron-chlorinated 1,2-azaborines and a novel class of boron-bound 1,2-azaborinyl nitrites, respectively. Comparison between the relative stabilities of C(3)-bound and C(5)-bound Wheland intermediates of different electrophilic substitution reactions of 1,2-azaborines further suggests that the preference of the C(3)- over C(5)-substitution decreases with decreasing electrophilicity of the attacking group.
authors.affiliation: REQUIMTE, Fac. de Ciências da Saúde, Universidade Fernando Pessoa, Rua Carlos da Maia, 296, 4200-150 Porto, Portugal.
authors.forename: Pedro J
authors.initials: PJ
authors.lastname: Silva
authors.forename: Maria João
authors.initials: MJ
authors.lastname: Ramos
mesh_terms: D000215:Acylation; D001372:Aza Compounds / Q000737:chemistry*; D001554:Benzene / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D009566:Nitrates / Q000737:chemistry; D010084:Oxidation-Reduction; D011789:Quantum Theory; D055672:Static Electricity; D013816:Thermodynamics
chemical_list: D001372:Aza Compounds; D009566:Nitrates; D001554:Benzene