Scholarlink

<p>Although significant developments are made in non-noble metal catalysts for N-alkylation of nitroarenes with alcohols via borrowing hydrogen strategy, obtaining catalysts with superior activity, reusability and broad substrate scope under mild reaction conditions remains challenging. Single-atom catalysts (SACs) hold unique coordination/electron structures, to be the potential candidates for this reaction. In this study, we firstly and creatively fabricate bio-inspired Zn SACs with asymmetric Zn-N<sub>2</sub>O<sub>2</sub> sites by utilizing the natural skeleton of biomass chitosan (denoted as Zn/CS), and achieve the first instance of heterogeneous Zn SACs in borrowing hydrogen reaction between nitroarenes and alcohols. The results reveal that the asymmetric Zn-N<sub>2</sub>O<sub>2</sub> sites induced by natural skeleton (like ligands) and nanoporous structure of Zn/CS significantly promote the N-alkylation efficiency of nitroarenes with alcohols. Notably, the Zn/CS exhibits the highest turnover frequency (TOF) among the reported heterogeneous catalysts, as well as wide substrate scope (56 examples) and excellent reusability. Furthermore, the catalytic pathway/mechanism is investigated by combing theoretical calculations, which reveals that the asymmetric Zn-N<sub>2</sub>O<sub>2</sub> sites with electron-deficient character can facilitate the formation of Zn-H and Zn-O bonds between Zn/CS and Ph-CH<sub>2</sub>O<sup>−</sup>, thus easily generating the transition state Ph-CH<sub>2</sub>O* and driving the whole reaction.</p>

错误：搜索内容不能为空，请输入英文关键词
错误：关键词超出字数限制，请精简
高级检索

Bio-inspired asymmetric Zn-N2O2 single-atom catalysts via natural skeleton for efficient N-alkylation of nitroarenes with alcohols

  • 期刊论文

  • 出版模式：

    开放获取

  • 发表日期：

    2026年3月5日

查看全文
  • Yu Huang,
  • Yan Li,
  • Xiaogang Yin,
  • Qiudi Zhu,
  • Mei He,
  • Xueqin Chang,
  • Xuefei Liu,
  • Wu Li,
  • Aiwen Lei,
  • Xianglin Pei

摘要

Although significant developments are made in non-noble metal catalysts for N-alkylation of nitroarenes with alcohols via borrowing hydrogen strategy, obtaining catalysts with superior activity, reusability and broad substrate scope under mild reaction conditions remains challenging. Single-atom catalysts (SACs) hold unique coordination/electron structures, to be the potential candidates for this reaction. In this study, we firstly and creatively fabricate bio-inspired Zn SACs with asymmetric Zn-N2O2 sites by utilizing the natural skeleton of biomass chitosan (denoted as Zn/CS), and achieve the first instance of heterogeneous Zn SACs in borrowing hydrogen reaction between nitroarenes and alcohols. The results reveal that the asymmetric Zn-N2O2 sites induced by natural skeleton (like ligands) and nanoporous structure of Zn/CS significantly promote the N-alkylation efficiency of nitroarenes with alcohols. Notably, the Zn/CS exhibits the highest turnover frequency (TOF) among the reported heterogeneous catalysts, as well as wide substrate scope (56 examples) and excellent reusability. Furthermore, the catalytic pathway/mechanism is investigated by combing theoretical calculations, which reveals that the asymmetric Zn-N2O2 sites with electron-deficient character can facilitate the formation of Zn-H and Zn-O bonds between Zn/CS and Ph-CH2O−, thus easily generating the transition state Ph-CH2O* and driving the whole reaction.