期刊
ORGANIC & BIOMOLECULAR CHEMISTRY
卷 20, 期 43, 页码 8443-8453出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d2ob01623k
关键词
-
资金
- NSF [CNS-0619508]
Thermally promoted cycloaddition reactions of tropone-3,4-dimethylester and cyclopentadiene have been investigated computationally, revealing that substitution of the tropone component with methyl esters leads to lower energy barriers, higher thermodynamic driving forces, and a greater number of possible reaction pathways.
Thermally promoted cycloaddition reactions of tropone-3,4-dimethylester and cyclopentadiene have been investigated using density functional theory calculations at the M06-2X level and the CBS-QB3 method. The reaction shares several characteristics with previously investigated cycloadditions involving unsubstituted tropone and cyclopentadiene, however substitution of the tropone component with methyl esters results in lower transition state free energy barriers, greater thermodynamic driving forces, and a significant increase in the number of possible pericyclic reaction pathways. Eighteen different [4 + 2], [6 + 4], or [8 + 2] cycloaddition products are possible and many of the initially formed cycloadducts can be interconverted through Cope or Claisen rearrangements. Of the many possible cycloaddition products only two are predicted to form: the exo-[6 + 4] product and one [4 + 2] product where the substituted tropone appears to be the diene. The two computationally predicted products are the same as the two that are observed experimentally, however computations indicate that both products result from ambimodal processes rather than single-step (monomodal) cycloaddition pathways.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据