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<p>The functionalization of recalcitrant chemical bonds that require extreme reduction potentials is often thwarted by the absence of a defined reaction field to control potent intermediates. Conventional multiphoton photocatalysis generates super-reductants, whose immense energy dissipates through chaotic, diffusion-controlled pathways. Herein, an “association-gated” strategy is introduced that constructs sequential electron donor–acceptor complexes as programmable reaction microenvironments. This system initially captures a single photon through its sulfide/naphthalene monoimide complex. The resulting naphthalene monoimide radical anion serves as a scaffold to pre-organize the haloarene substrate into a second, distinct electron donor–acceptor complex, creating a reaction pocket for the final, energy-storing excitation. Such supramolecular confinement generates an extreme reducing potential at the carbon–halogen bond, suppressing both diffusive side-reactions and parasitic hydrogen atom transfer from amine donors. This unlocks a broad scope of transformations under air-tolerant conditions, providing a versatile tool for late-stage diversification.</p>

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Association-gated multiphoton activation of inert haloarenes via sequential electron donor–acceptor assembly

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年7月22日

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  • Kakeru Matsukuma,
  • Masanori Tayu,
  • Kento Muto,
  • Ryota Itai,
  • Masahiro Noji,
  • Satoshi Hayashi,
  • Sayaka Ohrui,
  • Nozomi Saito

摘要

The functionalization of recalcitrant chemical bonds that require extreme reduction potentials is often thwarted by the absence of a defined reaction field to control potent intermediates. Conventional multiphoton photocatalysis generates super-reductants, whose immense energy dissipates through chaotic, diffusion-controlled pathways. Herein, an “association-gated” strategy is introduced that constructs sequential electron donor–acceptor complexes as programmable reaction microenvironments. This system initially captures a single photon through its sulfide/naphthalene monoimide complex. The resulting naphthalene monoimide radical anion serves as a scaffold to pre-organize the haloarene substrate into a second, distinct electron donor–acceptor complex, creating a reaction pocket for the final, energy-storing excitation. Such supramolecular confinement generates an extreme reducing potential at the carbon–halogen bond, suppressing both diffusive side-reactions and parasitic hydrogen atom transfer from amine donors. This unlocks a broad scope of transformations under air-tolerant conditions, providing a versatile tool for late-stage diversification.