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PreprintCC BY-NC-NDChemRxiv

Dinuclear Gold Photocatalyzed Atom-Transfer σ-Bond Metathesis and Sequential Heck-type Coupling

Abstract

A dinuclear gold photocatalytic approach for strain-release σ-bond metathesis has been developed by combining inner-sphere electron transfer (ISET) and radical ligand transfer (RLT) mechanisms. This strategy facilitates atom-transfer reactions via C–I bond cleavage, radical translocation, and ligand transfer, yielding a wide range of spirocyclobutyl oxindoles with excellent substrate diversity and atom economy. Additionally, the produced C(sp 3 )–I bond functions as a versatile handle for selective Heck-type coupling with alkenes. Mechanistic investigations indicate a combined ISET-RLT pathway, where sequential excitation and excited-state aurophilic interactions between high-valent gold centers weaken the Au–I bond and enable ligand transfer. Gramscale synthesis and further derivatizations highlight the synthetic utility of this methodology.

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BibTeX
@misc{pal2026dinuclear,
  title = {{Dinuclear Gold Photocatalyzed Atom-Transfer σ-Bond Metathesis and Sequential Heck-type Coupling}},
  author = {Sourav Pal and Pintu Kumbhakar and Theertha Babu T and Malekul Islam and Suman De Sarkar},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15009073/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009073/v1},
  note = {CC BY-NC-ND},
}
RIS
TY  - UNPB
TI  - Dinuclear Gold Photocatalyzed Atom-Transfer σ-Bond Metathesis and Sequential Heck-type Coupling
AU  - Sourav Pal
AU  - Pintu Kumbhakar
AU  - Theertha Babu T
AU  - Malekul Islam
AU  - Suman De Sarkar
PY  - 2026
DA  - 2026/09/18
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15009073/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009073/v1
AB  - A dinuclear gold photocatalytic approach for strain-release σ-bond metathesis has been developed by combining inner-sphere electron transfer (ISET) and radical ligand transfer (RLT) mechanisms. This strategy facilitates atom-transfer reactions via C–I bond cleavage, radical translocation, and ligand transfer, yielding a wide range of spirocyclobutyl oxindoles with excellent substrate diversity and atom economy. Additionally, the produced C(sp 3 )–I bond functions as a versatile handle for selective Heck-type coupling with alkenes. Mechanistic investigations indicate a combined ISET-RLT pathway, where sequential excitation and excited-state aurophilic interactions between high-valent gold centers weaken the Au–I bond and enable ligand transfer. Gramscale synthesis and further derivatizations highlight the synthetic utility of this methodology.
ER  -