Palladium-catalyzed C-F activation of polyfluoronitrobenzene derivatives in Suzuki-Miyaura coupling reactions.
Highly fluorinated nitrobenzene derivatives are suitable substrates for palladium-catalyzed C-F bond arylation using readily available palladium catalysts under both conventional heating and microwave conditions. Arylation occurs ortho to the nitro group offering a synthetic route to polyfluorinated 2-arylnitrobenzene systems. The regiochemistry of the arylation reactions suggests that there is a significant directing interaction between the nitro group and the incoming nucleophilic palladium catalyst which is facilitated by the presence of several fluorine atoms attached the ring. Investigations into the regioselectivity and reactivity of several tetrafluoro- and trifluoronitrobenzene derivatives provides further evidence for the highly nucleophilic character of the oxidative addition step in contrast to the concerted mechanism of more conventional Suzuki-Miyaura coupling reactions involving aryl iodides and bromides.
Cargill
Matthew R
MR
Department of Chemistry, Durham University, South Road, Durham DH1 3LE, UK.
Sandford
Graham
G
Tadeusiak
Andrezj J
AJ
Yufit
Dmitrii S
DS
Howard
Judith A K
JA
Kilickiran
Pinar
P
Nelles
Gabrielle
G
D002384:Catalysis; D018360:Crystallography, X-Ray; D006358:Hot Temperature; D008872:Microwaves; D008958:Models, Molecular; D015394:Molecular Structure; D009578:Nitrobenzenes / Q000138:chemical synthesis* / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*
D009578:Nitrobenzenes; D009942:Organometallic Compounds; D010165:Palladium