Oxygen-enabled Fe-catalyzed heteroatom α-C(sp3)–H functionalization with nucleophiles

Abstract

Here, we report an iron-catalyzed aerobic transformation that activates N/O/S-α-C(sp3)–H bonds under blue light irradiation, forming hemiacetal-type analogues, amenable for trapping with diverse commercially available N-, O-, S-, and C-nucleophiles. The method achieves azolation, amination, acetalization, hydroxylation, thiolation, alkylation, and arylations across ethers, thioethers and pyrrolidines with high chemoselectivity and regioselectivity. Mechanistic studies indicate that this system synergizes iron-catalyzed photoinduced LMCT, followed by chlorine radical-initiated HAT and subsequent O2 trapping of the resulting alkyl radicals to afford key hemiacetal-type intermediates. Significantly, FeCl3 serves a triple catalytic role by generating chlorine radicals, functioning as a redox shuttle and acting as a Lewis acid activator.

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BibTeX RIS

BibTeX

@article{zhou2026oxygenenabled,
  title = {{Oxygen-enabled Fe-catalyzed heteroatom α-C(sp3)–H functionalization with nucleophiles}},
  author = {Xinlong Zhou and Jiayin Li and Nan Huang and Jingjing Zhao and Baokun Qiao and Hegui Gong and Pan Li},
  journal = {Chemical Science},
  year = {2026},
  month = sep,
  doi = {10.1039/d6sc05655e},
  url = {https://doi.org/10.1039/d6sc05655e},
  note = {CC BY 3.0},
}

RIS

TY  - JOUR
TI  - Oxygen-enabled Fe-catalyzed heteroatom α-C(sp3)–H functionalization with nucleophiles
AU  - Xinlong Zhou
AU  - Jiayin Li
AU  - Nan Huang
AU  - Jingjing Zhao
AU  - Baokun Qiao
AU  - Hegui Gong
AU  - Pan Li
PY  - 2026
DA  - 2026/09/18
JO  - Chemical Science
DO  - 10.1039/d6sc05655e
UR  - https://doi.org/10.1039/d6sc05655e
AB  - Here, we report an iron-catalyzed aerobic transformation that activates N/O/S-α-C(sp3)–H bonds under blue light irradiation, forming hemiacetal-type analogues, amenable for trapping with diverse commercially available N-, O-, S-, and C-nucleophiles. The method achieves azolation, amination, acetalization, hydroxylation, thiolation, alkylation, and arylations across ethers, thioethers and pyrrolidines with high chemoselectivity and regioselectivity. Mechanistic studies indicate that this system synergizes iron-catalyzed photoinduced LMCT, followed by chlorine radical-initiated HAT and subsequent O2 trapping of the resulting alkyl radicals to afford key hemiacetal-type intermediates. Significantly, FeCl3 serves a triple catalytic role by generating chlorine radicals, functioning as a redox shuttle and acting as a Lewis acid activator.
SN  - 2041-6520
SN  - 2041-6539
ER  -

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