Gu Wenhao, Zhang John Z H
Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, Shanghai Key Laboratory of Green Chemistry & Chemical Process, School of Chemistry and Molecular Engineering, East China Normal University at Shanghai, 200062, China.
Faculty of Synthetic Biology and Institute of Synthetic Biology, Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen, 518055, China.
Phys Chem Chem Phys. 2024 Mar 20;26(12):9636-9644. doi: 10.1039/d3cp06320h.
In this work, we report a density functional theory (DFT) study and a dynamical trajectory study of substituent effects on the ambimodal [6+4]/[4+2] cycloaddition proposed for 1,3,5,10,12-cycloheptadecapentaene, referred to as cycloheptadecapentaene. The proposed cycloaddition proceeds through an ambimodal transition state, which results in both a [6+4] adduct a [4+2] adduct directly. The [6+4] adduct can be readily converted to the [4+2] adduct a Cope rearrangement. We study the selectivity of the reaction with regard to the position of substituents, steric effects of substituents, and electronic effects of substituents. In the dynamical trajectory study, we find that nitro-substituted reactants lead to a new product from the ambimodal transition state the hetero Diels-Alder reaction, and this new product can then be converted to a [4+2] adduct by a hetero [3, 3]-sigmatropic rearrangement. These results may provide insights for designing more bridged heterocyclic compounds.
在本研究中，我们报告了对1,3,5,10,12 - 环十七碳五烯（简称环十七碳五烯）所提出的双峰[6 + 4]/[4 + 2]环加成反应中取代基效应的密度泛函理论（DFT）研究和动力学轨迹研究。所提出的环加成反应通过双峰过渡态进行，该过渡态直接产生[6 + 4]加合物和[4 + 2]加合物。[6 + 4]加合物可通过Cope重排轻松转化为[4 + 2]加合物。我们研究了反应在取代基位置、取代基空间效应和取代基电子效应方面的选择性。在动力学轨迹研究中，我们发现硝基取代的反应物从双峰过渡态产生一种新产物——杂环Diels - Alder反应，然后这种新产物可通过杂[3, 3] - 西格玛重排转化为[4 + 2]加合物。这些结果可能为设计更多桥连杂环化合物提供见解。
