A unified strategy for α-alkoxyalkyl radical generation via pinacol boronic ester precursors

Abstract

A general method to generate α-alkoxyalkyl radicals from pinacol boronic ester precursors (R-Bpin) has been developed. These radical precursors are stable in air, easy to prepare, and readily accessible via Matteson homologation followed by a 1,2-metallate shift with a broad range of metal alkoxides. The key step is a transesterification with catechol methyl borate (MeOBcat), converting the inert Bpin species into a radical-active Bcat intermediate, which then undergoes nucleohomolytic substitution at boron to release the desired radical. This approach is practical, scalable (demonstrated at 4 mmol scale), and broadly applicable. It avoids toxic reagents and expensive photocatalysts, offering a straightforward route to ether-containing molecules relevant to the synthesis of natural product and bioactive compounds.

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BibTeX

@article{andrejoyaux2026unified,
  title = {{A unified strategy for α-alkoxyalkyl radical generation via pinacol boronic ester precursors}},
  author = {Emy André-Joyaux and Lise Benoist and Agathe Fayolle and Fabrice Dénès and Philippe Renaud},
  journal = {Organic Chemistry Frontiers},
  year = {2026},
  month = sep,
  doi = {10.1039/d6qo01025c},
  url = {https://nantes-universite.hal.science/hal-05853697v1},
  note = {CC BY 4.0},
}

RIS

TY  - JOUR
TI  - A unified strategy for α-alkoxyalkyl radical generation via pinacol boronic ester precursors
AU  - Emy André-Joyaux
AU  - Lise Benoist
AU  - Agathe Fayolle
AU  - Fabrice Dénès
AU  - Philippe Renaud
PY  - 2026
DA  - 2026/09/15
JO  - Organic Chemistry Frontiers
DO  - 10.1039/d6qo01025c
UR  - https://nantes-universite.hal.science/hal-05853697v1
AB  - A general method to generate α-alkoxyalkyl radicals from pinacol boronic ester precursors (R-Bpin) has been developed. These radical precursors are stable in air, easy to prepare, and readily accessible via Matteson homologation followed by a 1,2-metallate shift with a broad range of metal alkoxides. The key step is a transesterification with catechol methyl borate (MeOBcat), converting the inert Bpin species into a radical-active Bcat intermediate, which then undergoes nucleohomolytic substitution at boron to release the desired radical. This approach is practical, scalable (demonstrated at 4 mmol scale), and broadly applicable. It avoids toxic reagents and expensive photocatalysts, offering a straightforward route to ether-containing molecules relevant to the synthesis of natural product and bioactive compounds.
SN  - 2052-4110
SN  - 2052-4129
ER  -

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