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

Authors

George C. Shields, Bucknell UniversityFollow
Frank C. Pickard IV
Rebecca L. Shepherd
Amber E. Gillis
Meghan E. Dunn
Steven Feldgus
Karl N. KirschnerFollow
Mariappan Manoharan
Igor V. Alabugin

Publication Date

2006

Description

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.

Journal

The Journal of Physical Chemistry

Volume

110

Issue

7

First Page

2517

Last Page

2526

Department

Chemistry

Link to Published Version

http://dx.doi.org/10.1021/jp0562835

Recommended Citation

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.