Ortho effect in the Bergman cyclization: electronic and steric effects in hydrogen abstraction by 1-substituted naphthalene 5,8-diradicals

Abstract

We present a detailed theoretical study of geometries, electronic structure, and energies of transition states and intermediates completing the full Bergman cycloaromatization pathway of ortho-substituted enediynes with a focus on polar and steric contributions to the kinetics and thermodynamics of hydrogen abstraction. This study provides a rare unambiguous example of remote substitution that affects reactivity of a neutral reactive intermediate through an sigma framework.