Modulation of Prins Cyclization by Vibrational Strong Coupling
Modulation of Prins Cyclization by Vibrational Strong Coupling
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DOI：
10.1002/anie.201915632
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发表时间：
2020-02-18
影响因子：
16.6
通讯作者：
Uji-i, Hiroshi
中科院分区：
文献类型：
--
作者：
Hirai, Kenji;Takeda, Rie;Uji-i, Hiroshi
光分子强耦合是近十年来出现的一种控制化学反应的新方法。几年前，人们发现化学反应性可以通过振动强耦合（VSC）来改变。到目前为止，只有有限数量的反应在VSC下进行了研究，包括溶剂分解和脱保护反应。在这里，VSC对一系列醛和酮进行Prins环化反应，在药物化学中的一个重要的合成步骤，的影响进行了研究。观察到反应物羰基伸缩基团的二阶速率常数随VSC的降低。我们还观察到由于VSC的活化能增加，但活化焓和熵的比例变化，表明反应途径没有实质性的变化。将普通环加成反应添加到VSC修饰的化学反应的稳定性中是建立VSC作为合成化学的真正工具的另一个步骤。
Light-molecule strong coupling has emerged within the last decade as a new method to control chemical reactions. A few years ago it was discovered that chemical reactivity could be altered by vibrational strong coupling (VSC). Only a limited number of reactions have been investigated under VSC to date, including solvolysis and deprotection reactions. Here the effect of VSC on a series of aldehydes and ketones undergoing Prins cyclization, an important synthetic step in pharmaceutical chemistry, is investigated. A decrease of the second-order rate constant with VSC of the reactant carbonyl stretching groups is observed. We also observe an increased activation energy due to VSC, but proportional changes in activation enthalpy and entropy, suggesting no substantive change in reaction pathway. The addition of common cycloaddition reactions to the stable of VSC-modified chemical reactions is another step towards establishing VSC as a genuine tool for synthetic chemistry.