Skip to content
DraconiticResearch
Search Sources API
194,161 studies31 sourcesUpdated 25 min ago
PreprintCC BYChemRxiv

Substrate-Controlled Electrophilic Fluorination of Alkenyl Boronates: Direct versus 1,2- H -Migrative Fluorodeboronation

  • Oleksandr S. Liashuk1,2
  • Oleksandr P. Demchuk3,4
  • Varvara Trachova1,3
  • Illya Zahorniy1,3
  • Oleksandr Hryshchuk1,3
  • Tetiana Zubatiuk5,6
  • Andrii Kozytskyi1,3
  • Oleksandr Isayev5,6
  • Oleksandr O. Grygorenko1,2,3
6 affiliations
  1. 1Taras Shevchenko National University of Kyiv, Volodymyrska Street 60, Kyїv, Ukraine, 01601
  2. 2Enamine Scientific Research Institute, Winston Churchill Street 67, Kyїv, Ukraine, 02094
  3. 3Enamine Ltd., Winston Churchill Street 78, Kyїv, Ukraine, 02094
  4. 4Institute of Organic Chemistry, NAS of Ukraine, Akademik Kukhar Street 5, Kyїv, Ukraine, 02066
  5. 5Department of Chemistry
  6. 6Mellon College of Science, Carnegie Mellon University
Open at sourcePDFDOICite

Abstract

A general fluorodeboronation protocol that converts readily available alkenyl boronates into fluorinated alkenes under mild aqueous biphasic conditions is proposed. The method employs 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis-tetrafluoroborate (F-TEDA) as a fluorine source in the presence of KHF 2 , providing broad access to functionalized alkenyl fluorides from β-substituted and β,β-disubstituted alkenyl boronates, including cyclic, heterocyclic, aryl-, heteroaryl-, and alkyl-substituted derivatives, with good functional-group tolerance and preparative scalability. In contrast, αsubstituted alkenyl boronates displayed divergent reactivity, furnishing allylic fluorides through a rearrangement pathway. Mechanistic experiments and DFT calculations support initial electrophilic fluorination of the C=C bond followed by either BF 3 elimination or 1,2-hydride shift, depending on the substitution pattern and stability of the resulting cationic intermediate.

Related

  1. A study towards the undirected fluorination and chlorination of cubane 1,4-diester
    Laly Donnier-Valentin, Robin Heinrich, Quentin Fevre-Renault +3
    Beilstein Journal of Organic ChemistryPeer-reviewedCC BY 4.0Full textPharmacology & toxicologyHAL
  2. Arene fluorination and trifluoromethylation enabled by tetravalent group 10 metals ('formally' NiIV, PdIV, PtIV)
    Luca Demonti, Hana Tabikh, Noel Nebra
    Coordination Chemistry ReviewsPeer-reviewedCC BY 4.0Full text1 citedPharmacology & toxicologyHAL
  3. Chemputing the synthesis and optimisation of arene fluorination in an automated platform
    Filippo Protti, Nathan Jiscoot, Nicholas Capittini +6
    ChemRxivPreprintCC BY-NC-NDFull textPharmacology & toxicologyChemRxiv
  4. Non-electrophilic TRPA1 modulator MNP-021 protects neuronal and glial function from diabetes-associated glucotoxicity and neuroinflammation.
    Alessandro De Carli, Carolina Filipponi, Beatrice Polini +17
    Journal of translational medicinePeer-reviewedCC BY-NC-NDFull textPhysiologyEurope PMCPMC
  5. Predictive Value of Left Atrial Strain Combined with Low-Voltage Substrate for Recurrence After Radiofrequency Catheter Ablation in Persistent Atrial Fibrillation
    Diagnostics (Basel, Switzerland)Peer-reviewedCC BYFull textGeneral medicineEurope PMC

Cite

BibTeXRIS
BibTeX
@misc{liashuk2026substratecontrolled,
  title = {{Substrate-Controlled Electrophilic Fluorination of Alkenyl Boronates: Direct versus 1,2- H -Migrative Fluorodeboronation}},
  author = {Oleksandr S. Liashuk and Oleksandr P. Demchuk and Varvara Trachova and Illya Zahorniy and Oleksandr Hryshchuk and Tetiana Zubatiuk and Andrii Kozytskyi and Oleksandr Isayev and Oleksandr O. Grygorenko},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15010429/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010429/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Substrate-Controlled Electrophilic Fluorination of Alkenyl Boronates: Direct versus 1,2- H -Migrative Fluorodeboronation
AU  - Oleksandr S. Liashuk
AU  - Oleksandr P. Demchuk
AU  - Varvara Trachova
AU  - Illya Zahorniy
AU  - Oleksandr Hryshchuk
AU  - Tetiana Zubatiuk
AU  - Andrii Kozytskyi
AU  - Oleksandr Isayev
AU  - Oleksandr O. Grygorenko
PY  - 2026
DA  - 2026/10/13
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15010429/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010429/v1
AB  - A general fluorodeboronation protocol that converts readily available alkenyl boronates into fluorinated alkenes under mild aqueous biphasic conditions is proposed. The method employs 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis-tetrafluoroborate (F-TEDA) as a fluorine source in the presence of KHF 2 , providing broad access to functionalized alkenyl fluorides from β-substituted and β,β-disubstituted alkenyl boronates, including cyclic, heterocyclic, aryl-, heteroaryl-, and alkyl-substituted derivatives, with good functional-group tolerance and preparative scalability. In contrast, αsubstituted alkenyl boronates displayed divergent reactivity, furnishing allylic fluorides through a rearrangement pathway. Mechanistic experiments and DFT calculations support initial electrophilic fluorination of the C=C bond followed by either BF 3 elimination or 1,2-hydride shift, depending on the substitution pattern and stability of the resulting cationic intermediate.
ER  -