American Chemical Society, The Journal of Physical Chemistry A, 7(110), p. 2517-2526, 2006
DOI: 10.1021/jp0562835
Full text: Download
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.