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<p>Alkenes difunctionalization reaction has been recognized as a highly important organic transformation. However, its application is significantly hindered by the reliance on homogeneous transition metal-assisted radical addition, as well as the need for additional oxidants. In this study, we report that azido-hydroxylation of alkenes can be efficiently achieved by a heterogeneous photoelectrochemical (PEC) oxidation on the BiVO<sub>4</sub> photoanode, by using KN<sub>3</sub> as the azido source in the presence of HCO<sub>3</sub><sup>−</sup>. A wide range of alkene substrates featuring diverse substituent groups can be effectively oxidized to the corresponding product with an impressive product selectivity. Electrochemical and electron paramagnetic resonance (EPR) experiments confirmed that the high performance is assigned to the interaction of hetero-radicals produced from the oxidation of N<sub>3</sub><sup>−</sup> and HCO<sub>3</sub><sup>−</sup>. Transient spectroscopy dynamics experiments and density functional theory (DFT) analysis demonstrate that the addition order of two radical groups is attributed to their distinctive characteristics. The high reactivity of transient ·N<sub>3</sub> is preferentially added to the C=C double bond of alkene to form the carbon radical intermediate both kinetically and thermodynamically. The extended lifespan of persistent ·CO<sub>3</sub><sup>−</sup> can greatly increase the probability of paring the carbon radical intermediate, thus improving the selectivity of the azido-hydroxylation product. The present work provides a promising strategy for the difunctionalization of alkenes with the tandem addition of two radicals in the absence of homogeneous metal catalysis.</p>

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Highly efficient photoelectrochemical azido-hydroxylation of alkenes by metal-free tandem addition of two radicals

  • 期刊论文

  • 发表日期：

    2025年2月19日

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  • Jie Yang,
  • Yu Lei,
  • Youji Li,
  • Mengyu Duan,
  • Yufan Zhang,
  • Sipeng Yang,
  • Ge Tian,
  • Yukun Zhao,
  • Ran Duan,
  • Jikun Li,
  • Wenjing Song,
  • Chuncheng Chen,
  • Jincai Zhao

摘要

Alkenes difunctionalization reaction has been recognized as a highly important organic transformation. However, its application is significantly hindered by the reliance on homogeneous transition metal-assisted radical addition, as well as the need for additional oxidants. In this study, we report that azido-hydroxylation of alkenes can be efficiently achieved by a heterogeneous photoelectrochemical (PEC) oxidation on the BiVO4 photoanode, by using KN3 as the azido source in the presence of HCO3−. A wide range of alkene substrates featuring diverse substituent groups can be effectively oxidized to the corresponding product with an impressive product selectivity. Electrochemical and electron paramagnetic resonance (EPR) experiments confirmed that the high performance is assigned to the interaction of hetero-radicals produced from the oxidation of N3− and HCO3−. Transient spectroscopy dynamics experiments and density functional theory (DFT) analysis demonstrate that the addition order of two radical groups is attributed to their distinctive characteristics. The high reactivity of transient ·N3 is preferentially added to the C=C double bond of alkene to form the carbon radical intermediate both kinetically and thermodynamically. The extended lifespan of persistent ·CO3− can greatly increase the probability of paring the carbon radical intermediate, thus improving the selectivity of the azido-hydroxylation product. The present work provides a promising strategy for the difunctionalization of alkenes with the tandem addition of two radicals in the absence of homogeneous metal catalysis.