Mechanistic insights into the ruthenium-catalyzed site-selective oxidation of alcohols
Mechanistic insights into the ruthenium-catalyzed site-selective oxidation of alcohols
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钌催化醇的位点选择性氧化的机理见解
DOI：
10.1039/c8qo00329g
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发表时间：
2018-08
影响因子：
5.4
通讯作者：
Fu Yao
中科院分区：
文献类型：
--
作者：
Wang Bing;Jiang Julong;Yu Haizhu;Fu Yao
醇的位置选择性氧化由于其在天然产物转化为增值化学品方面的潜在应用而引起了广泛的研究兴趣。本文采用离散傅里叶变换（DFT）计算方法，系统地研究了钌催化醇的选择性氧化机理。研究发现，该反应是通过球内途径进行的，包括ru -烷氧配合物的形成、β-H的消除（生成Ru-H配合物和酮）、Ru-H配合物的氢化物转移到丙酮以及异丙醇的质子化。根据底物的性质，β-H消去和异丙醇的质子化都是反应速率的决定步骤。羟基周围大的位阻和低的电子密度会增加β-H消除的势垒，而邻近的配位基则有相反的作用。同时，氧化产物的相对稳定性也影响着整个屏障。上述因素都影响了羟基在不同环境下的选择性。此外，对多羟基络合物的反应位点进行了较好的预测，证明了理论结论在实际应用中的潜力。
The site-selective oxidation of alcohols has attracted extensive research interest due to its potential application in the conversion of natural products to value-added chemicals. Herein, the mechanism of the ruthenium-catalyzed site-selective Oppenauer-type oxidation of alcohols has been systematically investigated by DFT calculations. It was found that this reaction proceeds via an inner-sphere pathway, which involves the formation of the Ru–alkoxide complex, the β-H elimination (which generates a Ru–H complex and ketone), the hydride transfer from the Ru–H complex to acetone, and the protonation of isopropoxide. It was found that both the β-H elimination and the protonation of isopropoxide can be the rate-determining steps, depending on the properties of the substrate. Large steric hindrance and low electron density around the hydroxyl group would increase the barrier of β-H elimination, while an adjacent coordinating group has the opposite effect. Meanwhile, the relative stability of the oxidation product also weighs on the overall barrier. All the above factors contribute to the selectivity of the hydroxyls in different environments. In addition, the reactive site in a polyhydroxy complex is well predicted, demonstrating the potential of theoretical conclusions in practical applications.
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作者：
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通讯作者：
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影响因子：
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作者：
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DOI：
10.1039/9781782621652
发表时间：
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期刊：
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影响因子：
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DOI：
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发表时间：
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期刊：
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影响因子：
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