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

Authors

Frank C. Pickard
R. L. Shepherd
A. E. Gillis
Meghan E. Dunn
Steven Feldgus
Karl N. Kirschner
George C. Shields, Furman UniversityFollow
M. Alabugin Manoharan
V. I.

ACS Citation

Pickard, F. C.; Shepherd, R. L.; Gillis, A. E.; Dunn, M. E.; Feldgus, S.; Kirschner, K. N.; Shields, G. C.; Manoharan, M.; Alabugin, I. V. Ortho Effect in the Bergman Cyclization: Electronic and Steric Effects in Hydrogen Abstraction by 1-Substituted Naphthalene 5,8-Diradicals. J. Phys. Chem. A 2006, 110 (7), 2517-€“2526.

Version of Record

10.1021/jp0562835

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.

Source Name

Journal of Physical Chemistry A

Publication Date

2006

Volume

110

Issue

7

Page(s)

2517-2526

Document Type

Citation

Citation Type

Article