How Chemical Environment Activates Anthralin and Molecular Oxygen for Direct Reaction
How Chemical Environment Activates Anthralin and Molecular Oxygen for Direct Reaction
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化学环境如何激活蒽林和分子氧进行直接反应
DOI：
10.1021/acs.joc.9b03133
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
DuBois, Jennifer L.
中科院分区：
文献类型：
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作者：
Ellis, Emerald S.;MacHale, Luke T.;Szilagyi, Robert K.;DuBois, Jennifer L.
化学环境在促进蒽林/O2反应中的作用是用纯溶剂模拟非辅因子依赖性加氧酶的氨基酸而发现的。实验和计算结果突出了底物烯醇化物的重要性，该底物烯醇化物通过能量小的、逐步升级的步骤来获得，其中基态酮异构体互变异构为烯醇，然后通过溶剂电离。由此产生的离子对准备自发电子转移到O2。类似的活化可以在涉及O2的生物/非生物氧化中利用。
The role of the chemical environment in promoting anthralin/O2reactions was discovered using neat solvents to model the amino acids of a cofactor-independent oxygenase. Experimental and computational results highlight the importance of the substrate-enolate, which is accessed via energetically small, escalating steps in which the ground-state keto-isomer is tautomerized to an enol and then ionized by solvent. The resulting ion-pair is poised for spontaneous electron transfer to O2. Similar activation may be exploited in biological/nonbiological oxidations involving O2.