Details

Autor(en) / Beteiligte

• Shields, Benjamin J
• Doyle, Abigail G

Titel

Direct C(sp3)–H Cross Coupling Enabled by Catalytic Generation of Chlorine Radicals

Ist Teil von

• Journal of the American Chemical Society, 2016-10, Vol.138 (39), p.12719-12722

Ort / Verlag

United States: American Chemical Society

Erscheinungsjahr

2016

Quelle

MEDLINE

Beschreibungen/Notizen

• Here we report the development of a C­(sp3)–H cross-coupling platform enabled by the catalytic generation of chlorine radicals by nickel and photo­redox catalysis. Aryl chlorides serve as both cross-coupling partners and the chlorine radical source for the α-oxy C­(sp3)–H arylation of cyclic and acyclic ethers. Mechanistic studies suggest that photolysis of a Ni­(III) aryl chloride intermediate, generated by photo­redox-mediated single-electron oxidation, leads to elimination of a chlorine radical in what amounts to the sequential capture of two photons. Arylations of a benzylic C­(sp3)–H bond of toluene and a completely unactivated C­(sp3)–H bond of cyclohexane demonstrate the broad implications of this manifold for accomplishing numerous C­(sp3)–H bond functionalizations under exceptionally mild conditions.