Scholarlink

<p>Transition metal-catalysed carbene transfer reactions are some of the most widely used methods and facilitate a range of otherwise inaccessible chemistry. These transformations are generally promoted by precious-metal catalysts, so the use of inexpensive and less toxic iron complexes is under development. However, surprisingly little is known about the key intermediates. Here we report an iron-catalysed cascade reaction of alkyne-tethered diazo compounds, providing carbocycles with structural diversity and flexibility under mild conditions. Control experiments and density functional theory calculations unambiguously reveal two distinct reaction pathways catalysed by either Fe(II) or Fe(III) porphyrin complexes, which involve carbene and carbene radical intermediates, respectively. The structure of the key vinyl iron carbene intermediate, determined by X-ray crystallography, is provided. The utilization of a heterogeneous iron catalyst, FeP–CMP, demonstrates remarkable robustness, maintaining its catalytic efficacy even after recycling ten times. The synthetic utility of the reaction is demonstrated by the synthesis of polysubstituted arenes via a streamlined one-pot process.</p><p></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

Iron-catalysed carbene and carbene radical cascade reactions for the synthesis of carbocyclic molecules

  • 期刊论文

  • 发表日期：

    2026年2月20日

查看全文
  • Xinke Zhang,
  • Minghan Yao,
  • Kewei Chen,
  • Yuecheng Weng,
  • Wenhua Zhang,
  • Andreas W. Ehlers,
  • Bas de Bruin,
  • Xinfang Xu

摘要

Transition metal-catalysed carbene transfer reactions are some of the most widely used methods and facilitate a range of otherwise inaccessible chemistry. These transformations are generally promoted by precious-metal catalysts, so the use of inexpensive and less toxic iron complexes is under development. However, surprisingly little is known about the key intermediates. Here we report an iron-catalysed cascade reaction of alkyne-tethered diazo compounds, providing carbocycles with structural diversity and flexibility under mild conditions. Control experiments and density functional theory calculations unambiguously reveal two distinct reaction pathways catalysed by either Fe(II) or Fe(III) porphyrin complexes, which involve carbene and carbene radical intermediates, respectively. The structure of the key vinyl iron carbene intermediate, determined by X-ray crystallography, is provided. The utilization of a heterogeneous iron catalyst, FeP–CMP, demonstrates remarkable robustness, maintaining its catalytic efficacy even after recycling ten times. The synthetic utility of the reaction is demonstrated by the synthesis of polysubstituted arenes via a streamlined one-pot process.