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PreprintCC BY-NC-NDChemRxiv

Chromoselective Control for Aminoalkylation of CF3‑Alkenes through Low-Energy Photoredox Catalysis

  • Marine Le Stum1,2
  • Maria Eduarda Candido Thedy1,2
  • Taline Kerackian1,2
  • Jean-Christophe Cintrat1,2
  • Emmanuel Nicolas3
  • Laurence Grimaud4,5
  • Eugénie Romero1,2
5 affiliations
  1. 1SCBM
  2. 2Université Paris-Saclay
  3. 3CEA, CNRS, NIMBE, Université Paris-Saclay
  4. 4Département de Chimie
  5. 5École Normale Supérieure, PSL University, Sorbonne Université, CNRS
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Abstract

Recent advances in chromoselective photoredox catalysis have demonstrated that light wavelength can serve as a powerful and orthogonal reaction parameter, enabling divergent reactivity from a single catalytic system. Building on recent advances in the sequential decarboxylative/defluorinative aminoalkylation of trifluoromethyl-substituted alkenes, we report a divergent, wavelength-dependent strategy for the site-selective functionalization of N-arylglycines. High-throughput experimentation (HTE) was used to systematically screen photocatalysts and irradiation wavelengths to identify the most suitable divergent conditions. Interestingly, using [Ru(bpy)3]2+ as photocatalyst, irradiation with blue light promotes efficient difunctionalization of CF3-alkenes with N-arylglycines, affording monofluoroalkenyl-1,5-diamines, while switching the irradiation to red light enables selective monofunctionalization, delivering the corresponding gem-difluoroalkenyl amine intermediates exclusively under otherwise identical conditions, via a spin-forbidden transition pathway. This wavelength-governed switchable reactivity provides a powerful and tunable platform for the controlled radical modification of amino acids, expanding the synthetic utility of visible-light photoredox catalysis in divergent amine synthesis. Mechanistic investigations using photoelectrochemistry and TD-DFT have revealed notably a photo-excitation of intermediates, allowing for the second functionalization to whether happens or not, based on the irradiation wavelength used.

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Cite

BibTeXRIS
BibTeX
@misc{stum2026chromoselective,
  title = {{Chromoselective Control for Aminoalkylation of CF3‑Alkenes through Low-Energy Photoredox Catalysis}},
  author = {Marine Le Stum and Maria Eduarda Candido Thedy and Taline Kerackian and Jean-Christophe Cintrat and Emmanuel Nicolas and Laurence Grimaud and Eugénie Romero},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15010275/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010275/v1},
  note = {CC BY-NC-ND},
}
RIS
TY  - UNPB
TI  - Chromoselective Control for Aminoalkylation of CF3‑Alkenes through Low-Energy Photoredox Catalysis
AU  - Marine Le Stum
AU  - Maria Eduarda Candido Thedy
AU  - Taline Kerackian
AU  - Jean-Christophe Cintrat
AU  - Emmanuel Nicolas
AU  - Laurence Grimaud
AU  - Eugénie Romero
PY  - 2026
DA  - 2026/10/12
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15010275/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010275/v1
AB  - Recent advances in chromoselective photoredox catalysis have demonstrated that light wavelength can serve as a powerful and orthogonal reaction parameter, enabling divergent reactivity from a single catalytic system. Building on recent advances in the sequential decarboxylative/defluorinative aminoalkylation of trifluoromethyl-substituted alkenes, we report a divergent, wavelength-dependent strategy for the site-selective functionalization of N-arylglycines. High-throughput experimentation (HTE) was used to systematically screen photocatalysts and irradiation wavelengths to identify the most suitable divergent conditions. Interestingly, using [Ru(bpy)3]2+ as photocatalyst, irradiation with blue light promotes efficient difunctionalization of CF3-alkenes with N-arylglycines, affording monofluoroalkenyl-1,5-diamines, while switching the irradiation to red light enables selective monofunctionalization, delivering the corresponding gem-difluoroalkenyl amine intermediates exclusively under otherwise identical conditions, via a spin-forbidden transition pathway. This wavelength-governed switchable reactivity provides a powerful and tunable platform for the controlled radical modification of amino acids, expanding the synthetic utility of visible-light photoredox catalysis in divergent amine synthesis. Mechanistic investigations using photoelectrochemistry and TD-DFT have revealed notably a photo-excitation of intermediates, allowing for the second functionalization to whether happens or not, based on the irradiation wavelength used.
ER  -