Electrochemically Triggered Chain Reactions for the Conversion of Furan Derivatives
Electrochemically Triggered Chain Reactions for the Conversion of Furan Derivatives
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电化学引发的呋喃衍生物转化链式反应
DOI：
10.1002/anie.202016601
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发表时间：
2021
期刊：
影响因子：
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通讯作者：
Zhao, Yanyan
中科院分区：
文献类型：
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作者：
Chen, Rong;Yang, Cangjie;Zhou, Zefeng;Haeffner, Fredrik;Dersjant, Alinda;Dulock, Nicholas;Dong, Qi;He, Da;Jin, Jing;Zhao, Yanyan
我们报告了一种将生物质衍生的C5/C6化合物偶联到增值燃料前体的电化学方法。仅使用2%的当量电荷，2-甲基呋喃（2-MF）被氧化以产生阳离子自由基，其容易与3-己烯-2，5-二酮（2，5-二甲基呋喃的衍生物）反应以产生3-（5-甲基呋喃-2-基）己烷-2，5-二酮。该产物在一个步骤中以优异的产率转化为4-乙基壬烷（生物柴油/喷气燃料的组分）。重要的是，该反应对氧气不敏感，并且发现痕量的水促进反应。详细的机理研究证实了所提出的反应途径。该机制的关键是通过电化学实现的自由基生成。自由基在反应循环结束时再生，以确保链增长平均约100。47次，导致4700%的表观法拉第效率。
We report an electrochemical method for coupling biomass‐derived C5/C6 compounds to value‐added fuel precursors. Using only 2 % of equivalent charges, 2‐methylfuran (2‐MF) was oxidized to yield a cation radical, which readily reacted with 3‐hexene‐2,5‐dione, a derivate of 2,5‐dimethylfuran, to produce 3‐(5‐methylfuran‐2‐yl)hexane‐2,5‐dione. The product was converted to 4‐ethylnonane (a component of biodiesel/jet fuel) in a single step in excellent yield. Importantly, the reaction was not sensitive to oxygen, and a trace amount of water was found to promote the reaction. Detailed mechanistic studies confirmed the proposed reaction pathways. Key to the mechanism is the radical generation that is enabled by electrochemistry. The radical is regenerated at the end of a reaction cycle to ensure chain propagation for an average of ca. 47 times, resulting in an apparent Faradaic efficiency of 4700 %.