Work

Heterocyclizations at the Isocyanide Carbon: Mechanistic Insights into the 2-Isocyanoaniline to Benzimidazole Conversion

Year: 2026

Type: article

Abstract: High Resolution Image Download MS PowerPoint Slide Benzo-fused heteroazacycles can form through spontaneous cyclizations of phenylisocyanides bearing some electron donor substituents at the ortho position. Although such reactions have been known since the 1970s, a clear mechanistic understanding of these transformations remains absent. Here, we disclose a detailed computational analysis aimed at elucidating the more plausible mechanism for one of these cyclizations, the o -isocyanoaniline to benzimidazole conversion. Our results show that a transient 1,4-diazabutatriene could play a key role in this cyclization by enabling a reaction pathway of lower barrier than the unimolecular concerted process.

Source: The Journal of Organic Chemistry

DOI: 10.1021/acs.joc.5c02202

Authors: Mateo Alajarin, Marta Marin-Luna

Institution: Universidad de Murcia

Language: English

Topic: Organic Chemistry Cycloaddition Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,500

Funders: Fundación Séneca, Ministerio de Ciencia, Innovación y Universidades, European Regional Development Fund, Agencia Estatal de Investigación