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<p>The atom-by-atom manipulation of the core molecular framework has come into reality recently. In particular, the late-stage diversification of robust aza-arenes such as indole has been at the centre of research activity because of its importance in biological and pharmaceutical studies. The previous single-atom modifications of indoles were made possible through the insertion of a reactive nitrene species into the enamine-like C2–C3 bond, resulting in the incorporation of a new atom at the 3-position. Here we discovered an alternative reaction mode, in which the <i>N</i>-nitroso group underwent a sequential intramolecular translocation and deoxygenative rearrangement to afford regiochemically orthogonal 1,4-diazines that had been lacking in skeletal editing. This activation of the nearly inert aromatic C3–C9 bond was applicable to various indoles including bio-relevant molecules to furnish quinoxalines, a class of underexplored pharmacophores. The combined experimental and computational studies revealed the reaction mechanism for the unique selectivity pattern.</p><p></p>

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Regio-orthogonal single N-atom insertion into indoles via NO translocation

  • 期刊论文

  • 发表日期：

    2026年4月28日

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  • Mugeon Song,
  • Ilju Jeong,
  • Ha Eun Kim,
  • Jaeseong Jin,
  • Hyeon Moon,
  • Jeong Kyun Im,
  • Jungi Jung,
  • Junhyuk Jo,
  • Won-jin Chung

摘要

The atom-by-atom manipulation of the core molecular framework has come into reality recently. In particular, the late-stage diversification of robust aza-arenes such as indole has been at the centre of research activity because of its importance in biological and pharmaceutical studies. The previous single-atom modifications of indoles were made possible through the insertion of a reactive nitrene species into the enamine-like C2–C3 bond, resulting in the incorporation of a new atom at the 3-position. Here we discovered an alternative reaction mode, in which the N-nitroso group underwent a sequential intramolecular translocation and deoxygenative rearrangement to afford regiochemically orthogonal 1,4-diazines that had been lacking in skeletal editing. This activation of the nearly inert aromatic C3–C9 bond was applicable to various indoles including bio-relevant molecules to furnish quinoxalines, a class of underexplored pharmacophores. The combined experimental and computational studies revealed the reaction mechanism for the unique selectivity pattern.