C–H Arylation of Pyridines: High Regioselectivity as a Consequence of the Electronic Character of C–H Bonds and Heteroarene Ring

Citations Over TimeTop 10% of 2011 papers

Abstract

We report a new catalytic protocol for highly selective C-H arylation of pyridines containing common and synthetically versatile electron-withdrawing substituents (NO(2), CN, F and Cl). The new protocol expands the scope of catalytic azine functionalization as the excellent regioselectivity at the 3- and 4-positions well complements the existing methods for C-H arylation and Ir-catalyzed borylation, as well as classical functionalization of pyridines. Another important feature of the new method is its flexibility to adapt to challenging substrates by a simple modification of the carboxylic acid ligand or the use of silver salts. The regioselectivity can be rationalized on the basis of the key electronic effects (repulsion between the nitrogen lone pair and polarized C-Pd bond at C2-/C6-positions and acidity of the C-H bond) in combination with steric effects (sensitivity to bulky substituents).

Related Papers

• → Recent Advances in the Regioselective Synthesis of Pyrazoles(2011)73 cited
• → Remote substituent effects on regioselectivity in the Pauson–Khand reaction of 2-substituted norbornenes(2001)19 cited
• → N-CHLORO-2,3,4,4,5,6-HEXACHLOROCYCLOHEXA- 2,5-DIENYLIDENEAMINE AS A MILD AND HIGHLY REGIOSELECTIVE CHLORINATING REAGENT(2002)5 cited
• → β-Aminoenones in the regioselective synthesis of 1,3,5-trialkylpyrazoles. The influence of the substituents in the mechanism and the regioselectivity of the reaction(1998)12 cited
• → Regioselective Synthesis of 2-Substituted-4-Methylbenzimidazole Nucleosides(2005)2 cited