Ortho Effect in the Bergman Cyclization: Electronic and Steric Effects in Hydrogen Abstraction by 1-Substituted Naphthalene 5,8-Diradicals
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.
The Journal of Physical Chemistry
Shields, George C.; Pickard, Frank C. IV; Shepherd, Rebecca L.; Gillis, Amber E.; Dunn, Meghan E.; Feldgus, Steven; Kirschner, Karl N.; Manoharan, Mariappan; and Alabugin, Igor V.. "Ortho Effect in the Bergman Cyclization: Electronic and Steric Effects in Hydrogen Abstraction by 1-Substituted Naphthalene 5,8-Diradicals." The Journal of Physical Chemistry (2006) : 2517-2526.