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Ortho Effect in the Bergman Cyclization:  Electronic and Steric Effects in Hydrogen Abstraction by 1-Substituted Naphthalene 5,8-Diradicals

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journal contribution
posted 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.