非统计动力学效应对烯炔-烯丙基的 C2-C6 Diels-Alder 环化反应的影响。
Nonstatistical dynamic effects in the thermal C2-C6 Diels-Alder cyclization of enyne-allenes.
机构信息
Department of Chemistry and Biology, Universität Siegen, Adolf-Reichwein-Strasse, D-57068 Siegen, Germany.
出版信息
J Org Chem. 2013 Feb 15;78(4):1451-62. doi: 10.1021/jo302524a. Epub 2013 Feb 5.
The Diels-Alder (DA) reaction channel of the thermal C(2)-C(6) (Schmittel) cyclization of enyne-allenes is studied computationally and experimentally evaluating the influence of temperature on product ratios. Remote substituents at the alkyne terminus influence the mechanism of the C(2)-C(6)/DA cyclization steering it either to a stepwise or a concerted course. Temperature independent product ratios, selectivity of product formation, and computational results obtained at (U)BLYP/6-31G(d) level unveil a mechanism that is strongly controlled by nonstatistical dynamics.
烯炔-allenes 的热 C(2)-C(6) (Schmittel) 环化的 Diels-Alder (DA) 反应通道通过计算和实验进行了研究，评估了温度对产物比例的影响。炔烃末端的远程取代基影响 C(2)-C(6)/DA 环化的机制，使其偏向逐步或协同途径。在 (U)BLYP/6-31G(d) 水平下获得的温度无关的产物比、产物形成的选择性和计算结果揭示了一种受非统计动力学强烈控制的机制。
Zotero 插件