HCO3−-mediated highly efficient photoelectrochemical dioxygenation of arylalkenes: triple roles of HCO3−-derived radicals,Energy & Environmental Science

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HCO3−-mediated highly efficient photoelectrochemical dioxygenation of arylalkenes: triple roles of HCO3−-derived radicals
Energy & Environmental Science ( IF 32.4 ) Pub Date : 2023-11-13 , DOI: 10.1039/d3ee02948d
Jie Yang _{1,

2} , Yukun Zhao _{1,

2} , Mengyu Duan _{1,

2} , Chaoyuan Deng _{1,

2} , Yufan Zhang _{1,

2} , Yu Lei _{1,

2} , Jikun Li _{1,

2} , Wenjing Song _{1,

2} , Chuncheng Chen _{1,

2} , Jincai Zhao _{1,

2}

Affiliation

Alkene dioxygenation reactions are significant organic transformation process, but the direct oxidation of alkenes on photoanodes exhibits quite poor yields for dioxygenation products. Here, we report that the presence of bicarbonate in a heterogenous photoelectrochemical (PEC) cell can achieve efficient dioxygenation of alkenes under mild conditions. A broad range of alkene substrates with a variety of substitute groups can be effectively oxygenated to diols or α-hydroxy ketones, with a product yield of up to 89%. Furthermore, we identified that the diol product is formed via a peroxydiol intermediate. Spin-trap electron paramagnetic resonance (EPR) experiments show that the HCO₃⁻-derived radicals are important active species. Accordingly, we propose a triple role for formed HCO₃⁻-derived radicals in the dioxygenation of alkenes: attacking the C [double bond, length as m-dash]

C bond of the alkene to initiate the reaction, producing ˙CO₄⁻ active species for the formation of a peroxydiol intermediate, and reducing the peroxydiol to a diol. The present work provides a promising strategy for the transformation of alkenes with green radicals and paves the way for the application of HCO₃⁻ in PEC organic synthesis.

中文翻译：

HCO3−介导的芳基烯烃的高效光电化学双氧化：HCO3−衍生自由基的三重作用

烯烃双加氧反应是重要的有机转化过程，但烯烃在光阳极上的直接氧化显示出双加氧产物的产率相当差。在这里，我们报告说，异质光电化学（PEC）电池中碳酸氢盐的存在可以在温和条件下实现烯烃的有效双氧合。多种具有多种取代基的烯烃底物可以有效氧化为二醇或α-羟基酮，产品收率高达89%。此外，我们确定二醇产物是通过过氧二醇中间体形成的。自旋陷阱电子顺磁共振(EPR)实验表明HCO ₃^-衍生自由基是重要的活性物质。因此，我们提出了在烯烃双氧化反应中形成的HCO ₃^-衍生自由基的三重作用：攻击 [双键，长度为m-破折号]