Late-Stage Functionalization Using a Popular Titrating Agent: Aryl-Chlorides and -Fluorides Activation by the Diphenylacetic Acid Dianion

Aryl-chlorides and -fluorides are common building blocks, but their use in synthesis is limited by the high stability of their Ar-X bonds. The generation of aryl radicals via activation of strong Ar-X bonds is possible through the irradiation of tailor-made organic anions, which become reductants st...

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Bibliographic Details
Published in:Chemistry : a European journal 2024-11, p.e202403597
Main Authors: Cerveri, Alessandro, Russo, Giulia, Sparascio, Sara, Merli, Daniele, Maggi, Raimondo, Della Ca', Nicola, Lanzi, Matteo, Maestri, Giovanni
Format: Article
Language:English
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Summary:Aryl-chlorides and -fluorides are common building blocks, but their use in synthesis is limited by the high stability of their Ar-X bonds. The generation of aryl radicals via activation of strong Ar-X bonds is possible through the irradiation of tailor-made organic anions, which become reductants stronger than lithium metal. We report that the combination of visible light with the cheap diphenylacetic acid dianion is an even better tool, showing excellent activity across a variety of complex substrates and providing opportunities for late-stage drug modification. Ar-X bonds are chemoselectively activated in the presence of more easily reducible functions, such as Alk-Cl ones and carbonyl groups. These results pave the way to original synthetic strategies that would be otherwise considered impossible.
ISSN:0947-6539
1521-3765
1521-3765
DOI:10.1002/chem.202403597