Direct Deoxydehydration of Cyclic trans‐Diol Substrates: An Experimental and Computational Study of the Reaction Mechanism of Vanadium(V)‐based Catalysis**,ChemSusChem

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Direct Deoxydehydration of Cyclic trans‐Diol Substrates: An Experimental and Computational Study of the Reaction Mechanism of Vanadium(V)‐based Catalysis**
ChemSusChem ( IF 7.5 ) Pub Date : 2021-01-19 , DOI: 10.1002/cssc.202002594
Ebru Aksanoglu ₁ , Yee Hwee Lim ₂ , Richard Bryce ₃

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The deoxydehydration of carbohydrates represents a key target to leverage renewable biomass resources chemically. Using a vanadium(V)‐based catalyst, it was possible to directly deoxydehydrate cyclic trans‐diol substrates. Accompanying mechanistic characterisation of this process by density functional calculations pointed to an energetically tractable route for deoxydehydration of cyclic trans‐diol substrates involving stepwise cleavage of the diol C−O bonds via the triplet state; experimentally, this was supported by light dependence of the reaction. Calculations also indicated that cyclic cis‐diols and a linear diol substrate could additionally proceed by a concerted singlet DODH mechanism. This work potentially opens a new and cost‐effective way to efficiently convert carbohydrates of trans‐diol stereochemistry into alkenes.

中文翻译：

环状反式二酚底物的直接脱氧：基于钒（V）的催化反应机理的实验和计算研究**

碳水化合物的脱氧脱水是化学利用可再生生物质资源的关键目标。使用基于钒（V）的催化剂，可以直接对环状反式-二醇底物进行脱氧。通过密度泛函计算对该过程进行机械表征，指出了环状反式-二醇底物脱氧脱水的能量易处理路线，该过程涉及通过三重态逐步裂解二醇的C-O键；实验上，这是由反应的光依赖性支持的。计算还表明，循环顺式二醇和线性二醇底物还可以通过协同的单重态DODH机制进行。这项工作潜在地开辟了一种新的，具有成本效益的方式，可以有效地将反式-二醇立体化学的碳水化合物转化为烯烃。

更新日期：2021-03-23

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