Ortho Effect in the Bergman Cyclization: Electronic and Steric Effects in Hydrogen Abstraction by 1-Substituted Naphthalene 5,8-Diradicals
journal contributionposted on 23.02.2006, 00:00 by Pickard, Rebecca L. Shepherd, Amber E. Gillis, Meghan E. Dunn, Steven Feldgus, Karl N. Kirschner, George C. Shields, Mariappan Manoharan, Igor V. Alabugin
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 σ framework.
Read the peer-reviewed publication
CyclizationkineticDiradicalreactiveSteric EffectsBergman cycloaromatization pathwaySubstitutedOrtho EffectthermodynamicHydrogen AbstractiongeometrieNaphthalenetransition statesElectronicortho-substituted enediynesfocushydrogen abstractionσ frameworksubstitutionintermediatesteric contributions1-reactivity