A DFT Study on the Mechanism of Selective Formation of Substituted Azepines From 1‐Azabutadienes and Cyclopropanes
Abstract
Density Functional Theory (DFT) calculations were performed to elucidate the reaction mechanism of the Mg-catalyzed cyclization between an azadiene-type imine and a cyclopropane. The results reveal that the [4+3] cyclization pathway leading to azepine formation is both kinetically and thermodynamically preferred over the intuitively more accessible [3+2] pathway toward pyrrolidine formation. This unusual selectivity arises from the interplay of opposing electronic and steric effects, with steric effects ultimately dominating.
Fields of Study & Subjects
Cyclopropane Reaction Mechanisms
Catalytic Alkyne Reactions
Coordination Chemistry and Organometallics
Publication details
- Journal / source
- Chemistry - A European Journal
- Publisher
- Wiley
- Volume
- 32
- Issue
- 23
- Pages
- e70960–e70960
- Publication date
- 3 April 2026
- Language
- EN