Computational Studies on the Reactivity of Substituted 1,2-Dihydro-1,2-azaborines

• Type: Article in International Scientific Journal
• Date: 2009

Authors

Pedro J Silva (Author) Other; Maria Joao Ramos (Author) FCUP

Journal

Title: Journal of Organic Chemistry

Vol. 74

Pages: 6120-6129

ISSN: 0022-3263

Publisher: American Chemical Society

Indexing

ISI Web of Knowledge - 13 Citations

Scopus - 15 Citations

Scientific classification

FOS: Natural sciences > Chemical sciences

Other information

Authenticus ID: P-003-GPJ

DOI: 10.1021/jo900980d

Abstract (EN): 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.

Language: English

Type (Professor's evaluation): Scientific

No. of pages: 10