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PreprintCC BY-NC-NDChemRxiv

Light-driven metal-free thiocarbonyl – olefin metathesis: a general route to sterically hindered alkenes

  • Matthias Georges1,2
  • Gabriel Cormier1,2
  • Manuel Pedrón3,4,5
  • Antoine Laurens4,5
  • Timothé Ferrasse1,2
  • Ilaria Ciofini4,5
  • Thomas Boddaert1,2
5 affiliations
  1. 1ICMMO
  2. 2Université Paris-Saclay
  3. 3University of Zaragoza
  4. 4i-CLeHS
  5. 5Chimie ParisTech - PSL University
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Abstract

Highly substituted olefins are attractive scaffolds for molecular machines, optical materials and medicinal chemistry, whilst also serving as valuable intermediates in organic synthesis. However, their efficient and general preparation remains challenging, particularly in light of sustainability requirements. Here, we report a metal-free photochemical thiocarbonyl – olefin metathesis that provides access to a broad range of tri- and tetra-substituted alkenes, where light irradiation promotes both the regioselective formation and subsequent fragmentation of thietane intermediates. The scarcely explored photochemical cycloreversion of isolated thietanes was first thoroughly reinvestigated, leading to the proposal of a thioparabanate-photocatalyzed mechanism supported by Time-Dependent Density Functional Theory (TD-DFT) calculations. Then, the combination of this cycloreversion with a thia-Paternò_Büchi reaction into a photochemical cascade, enables the in situ generation of the thietane intermediate. Starting from thiocarbonyl substrates, independently prepared or generated in situ via Norrish type II fragmentation of phenacyl sulfide precursors, and diverse alkene partners, this light-mediated thiocarbonyl – olefin coupling offers an innovative and sustainable entry to a library of densely substituted olefins. The synthetic utility of this strategy is also demonstrated through its application to molecular motor templates synthesis.

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Cite

BibTeXRIS
BibTeX
@misc{georges2026lightdriven,
  title = {{Light-driven metal-free thiocarbonyl – olefin metathesis: a general route to sterically hindered alkenes}},
  author = {Matthias Georges and Gabriel Cormier and Manuel Pedrón and Antoine Laurens and Timothé Ferrasse and Ilaria Ciofini and Thomas Boddaert},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15010456/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010456/v1},
  note = {CC BY-NC-ND},
}
RIS
TY  - UNPB
TI  - Light-driven metal-free thiocarbonyl – olefin metathesis: a general route to sterically hindered alkenes
AU  - Matthias Georges
AU  - Gabriel Cormier
AU  - Manuel Pedrón
AU  - Antoine Laurens
AU  - Timothé Ferrasse
AU  - Ilaria Ciofini
AU  - Thomas Boddaert
PY  - 2026
DA  - 2026/10/14
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15010456/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010456/v1
AB  - Highly substituted olefins are attractive scaffolds for molecular machines, optical materials and medicinal chemistry, whilst also serving as valuable intermediates in organic synthesis. However, their efficient and general preparation remains challenging, particularly in light of sustainability requirements. Here, we report a metal-free photochemical thiocarbonyl – olefin metathesis that provides access to a broad range of tri- and tetra-substituted alkenes, where light irradiation promotes both the regioselective formation and subsequent fragmentation of thietane intermediates. The scarcely explored photochemical cycloreversion of isolated thietanes was first thoroughly reinvestigated, leading to the proposal of a thioparabanate-photocatalyzed mechanism supported by Time-Dependent Density Functional Theory (TD-DFT) calculations. Then, the combination of this cycloreversion with a thia-Paternò_Büchi reaction into a photochemical cascade, enables the in situ generation of the thietane intermediate. Starting from thiocarbonyl substrates, independently prepared or generated in situ via Norrish type II fragmentation of phenacyl sulfide precursors, and diverse alkene partners, this light-mediated thiocarbonyl – olefin coupling offers an innovative and sustainable entry to a library of densely substituted olefins. The synthetic utility of this strategy is also demonstrated through its application to molecular motor templates synthesis.
ER  -