Beyond strain release: Delocalisation-enabled organic reactivity
Beyond strain release: Delocalisation-enabled organic reactivity
复制标题
超越应变释放：离域化有机反应
DOI：
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Fernanda Duarte
中科院分区：
文献类型：
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作者：
A. Sterling;Russell T. Smith;Edward A Anderson;Fernanda Duarte
应变能一直被认为是有机反应的基本驱动力。然而，应变的释放本身是反应性的一个不足的预测，从等效应变能环丙烷和环丁烷不同的反应性可以看出。在这里，我们表明电子离域是一个关键因素，它与应变释放一起作用，以提高反应性，显著降低环丙烷、环炔和环烯烃断键所需的能量。热力学和离域参数的考虑解释了含有这些官能团的分子的相对反应速率，导致“离域层次”和准确预测激活障碍的经验法则模型。这些原理的含义在全合成、药物化学、聚合物科学和生物偶联中经常遇到的应变构建块反应的背景下得到了证明。
Strain energy has long been recognised as a fundamental driving force for organic reactions. However, the release of strain alone is an insufficient predictor of reactivity, as seen in the equivalent strain energies but disparate reactivity of cyclopropane and cyclobutane. Here we show that electronic delocalisation is a key factor that operates alongside strain release to boost reactivity, significantly lowering the energy required for bond-breaking in cyclopropanes, cycloalkynes and cycloalkenes. Consideration of thermodynamic and delocalisation parameters explains the relative rates of reaction of molecules containing these functional groups, leading to a ‘hierarchy of delocalisation’ and a rule-of-thumb model that accurately predicts activation barriers. The implications of these principles are demonstrated in the context of the reactions of strained building blocks commonly encountered in total synthesis, medicinal chemistry, polymer science and bioconjugation.
影响因子：
15
作者：
Agard, NJ;Prescher, JA;Bertozzi, CR
通讯作者：
Bertozzi, CR
影响因子：
46.2
作者：
Morten CJ;Byers JA;Van Dyke AR;Vilotijevic I;Jamison TF
通讯作者：
Jamison TF