Pickard Frank C, Shepherd Rebecca L, Gillis Amber E, Dunn Meghan E, Feldgus Steven, Kirschner Karl N, Shields George C, Manoharan Mariappan, Alabugin Igor V
Department of Chemistry, Hamilton College, Clinton, New York 13323, USA.
J Phys Chem A. 2006 Feb 23;110(7):2517-26. doi: 10.1021/jp0562835.
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.
我们对邻位取代烯二炔的完整伯格曼环化芳构化途径中的过渡态和中间体的几何结构、电子结构及能量进行了详细的理论研究，重点关注氢提取动力学和热力学中的极性和空间贡献。本研究提供了一个罕见的明确例子，即远程取代通过σ骨架影响中性反应中间体的反应活性。
