A Redox Strategy for Light-Driven, Out-of-Equilibrium Isomerizations and Application to Catalytic C-C Bond Cleavage Reactions
A Redox Strategy for Light-Driven, Out-of-Equilibrium Isomerizations and Application to Catalytic C-C Bond Cleavage Reactions
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DOI：
10.1021/jacs.8b12552
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发表时间：
2019-01-30
影响因子：
15
通讯作者：
Knowles, Robert R.
中科院分区：
文献类型：
--
作者：
Ota, Eisuke;Wang, Huaiju;Knowles, Robert R.
我们报告了一个通用的协议，光驱动的异构化环状脂肪醇的线性羰基化合物。这些反应通过醇O-H键的质子偶联电子转移活化，随后通过所得烷氧基自由基中间体的C-C β-断裂进行。在许多情况下，这些氧化还原中性异构化与显著的能量梯度相反地进行，产生比起始材料更不稳定的产物。提出了一种机制来合理化这种平衡外的行为，可以作为一个模型的设计，由激发态的氧化还原事件驱动的其他contrathermodynamic转换。
We report a general protocol for the light-driven isomerization of cyclic aliphatic alcohols to linear carbonyl compounds. These reactions proceed via proton-coupled electron-transfer activation of alcohol O-H bonds followed by subsequent C-C beta-scission of the resulting alkoxy radical intermediates. In many cases, these redox-neutral isomerizations proceed in opposition to a significant energetic gradient, yielding products that are less thermodynamically stable than the starting materials. A mechanism is presented to rationalize this out-of-equilibrium behavior that may serve as a model for the design of other contrathermodynamic transformations driven by excited-state redox events.