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<p>Installation of a functional group onto pyridines with predictable regiocontrol represents an appealing method for drug discovery programmes in the pharmaceutical industry. However, functionalization at the <i>meta</i> position of pyridines is often non-trivial owing to their inherent electronic properties, which commonly guide the reactions at the <i>ortho</i> and/or <i>para</i> positions. Here we report a method to enable regioselective migration of a peripheral aryl group on pyridines via 1,2-aryl migration of azacylohexadienyl radical intermediates generated by temporary dearomatization of the pyridine rings under photoredox catalysis. This process made it possible to transfer aryl substituents pre-installed at the <i>para</i> or <i>ortho</i> position of pyridines to the <i>meta</i> position by three different permutations: C4-to-C5, C4-to-C3 and C3-to-C2 aryl group transpositions. The present protocol exhibits broad functional group compatibility, offering streamlined access to a library of diverse <i>meta</i>-arylpyridines without the need for de novo synthesis.</p><p></p>

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Peripheral aryl group transposition on pyridines using photoredox catalysis

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年3月4日

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  • Eugene Yew Kun Tan,
  • Tian-Yu Peng,
  • Taku Wakabayashi,
  • Shunsuke Chiba

摘要

Installation of a functional group onto pyridines with predictable regiocontrol represents an appealing method for drug discovery programmes in the pharmaceutical industry. However, functionalization at the meta position of pyridines is often non-trivial owing to their inherent electronic properties, which commonly guide the reactions at the ortho and/or para positions. Here we report a method to enable regioselective migration of a peripheral aryl group on pyridines via 1,2-aryl migration of azacylohexadienyl radical intermediates generated by temporary dearomatization of the pyridine rings under photoredox catalysis. This process made it possible to transfer aryl substituents pre-installed at the para or ortho position of pyridines to the meta position by three different permutations: C4-to-C5, C4-to-C3 and C3-to-C2 aryl group transpositions. The present protocol exhibits broad functional group compatibility, offering streamlined access to a library of diverse meta-arylpyridines without the need for de novo synthesis.