title: C-H arylation of pyridines: high regioselectivity as a consequence of the electronic character of C-H bonds and heteroarene ring.
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).
authors.affiliation: Department of Chemistry, Columbia University, 3000 Broadway, New York, New York 10027, USA.
authors.forename: Pengfei
authors.initials: P
authors.lastname: Guo
authors.forename: Jung Min
authors.initials: JM
authors.lastname: Joo
authors.forename: Souvik
authors.initials: S
authors.lastname: Rakshit
authors.forename: Dalibor
authors.initials: D
authors.lastname: Sames
mesh_terms: D004583:Electrons; D015394:Molecular Structure; D011725:Pyridines / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D011725:Pyridines