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<p>Vicinal diamines—particularly unsymmetrical ones—are essential structural motifs in natural products, pharmaceuticals, and chiral catalysts. However, the regioselective synthesis of unsymmetrical vicinal diamines from unactivated alkenes remains a long-standing challenge. Herein, we report an iron-photocatalyzed ligand-to-metal charge-transfer (LMCT) strategy that enables the simultaneous generation of two nitrogen-centered radicals with distinct reactivities, allowing unsymmetrical diamination of alkenes under mild, additive-free conditions. The method features broad substrate scope, excellent regioselectivity, and compatibility with complex bioactive molecules, opening new avenues for late-stage amine diversification and drug discovery. Mechanistic studies suggest that an <i>in situ</i> Fe(III)-α-amido-oxy acid complex acts as the photoactive species, LMCT triggers O-centered radical formation, followed by decarboxylation/deacetonylation to generate an amidyl radical, which adds to alkenes and undergoes Fe-mediated azidyl transfer to afford unsymmetrical vicinal diamines.</p>

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Iron-photocatalyzed unsymmetrical diamination of alkenes via ligand-to-metal charge transfer

  • 期刊论文

  • 发表日期：

    2026年7月30日

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  • Hongshan Ni,
  • Yujun Li,
  • Ke Zheng

摘要

Vicinal diamines—particularly unsymmetrical ones—are essential structural motifs in natural products, pharmaceuticals, and chiral catalysts. However, the regioselective synthesis of unsymmetrical vicinal diamines from unactivated alkenes remains a long-standing challenge. Herein, we report an iron-photocatalyzed ligand-to-metal charge-transfer (LMCT) strategy that enables the simultaneous generation of two nitrogen-centered radicals with distinct reactivities, allowing unsymmetrical diamination of alkenes under mild, additive-free conditions. The method features broad substrate scope, excellent regioselectivity, and compatibility with complex bioactive molecules, opening new avenues for late-stage amine diversification and drug discovery. Mechanistic studies suggest that an in situ Fe(III)-α-amido-oxy acid complex acts as the photoactive species, LMCT triggers O-centered radical formation, followed by decarboxylation/deacetonylation to generate an amidyl radical, which adds to alkenes and undergoes Fe-mediated azidyl transfer to afford unsymmetrical vicinal diamines.