Direct C(sp3)-H Cross Coupling Enabled by Catalytic Generation of Chlorine Radicals.
J Am Chem Soc
; 138(39): 12719-12722, 2016 10 05.
Article
in En
| MEDLINE
| ID: mdl-27653738
ABSTRACT
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.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Main subject:
Carbon
/
Chlorine
/
Hydrogen
Language:
En
Journal:
J Am Chem Soc
Year:
2016
Document type:
Article
Affiliation country:
United States