Work

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

Year: 2026

Type: article

Abstract: A general method to generate α-alkoxyalkyl radicals from pinacol boronic ester precursors (R–Bpin) has been developed. Theses radical precursors are stable in air, easy to prepare, and readily accessible pinacol boronic esters via Matteson homologation followed by a 1,2-metalate 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 synthesis and bioactive compounds.

Source: Organic Chemistry Frontiers

DOI: 10.1039/d6qo01025c

Authors: Emy André-Joyaux, Lise Benoist, Agathe Fayolle, Fabrice Dénès, Philippe Renaud

Institutions: University of Bern, Centre National de la Recherche Scientifique, Chimie et Interdisciplinarité, Synthèse, Analyse, Modélisation, Université de Nantes, Nantes Université

Language: English

Topic: Radical Photochemical Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Funders: National Science Foundation, University of Bern, Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung, Centre National de la Recherche Scientifique

Awards: A dual wavelength X-ray single crystal diffractometer for accurate investigations at extreme conditions, G3643555740, Boron Mediated Reactions for the Total Synthesis and the Late Stage Modification of Natural Products, G6579006390