title: Arylation with unsymmetrical diaryliodonium salts: a chemoselectivity study.
abstract: Phenols, anilines, and malonates have been arylated under metal-free conditions with twelve aryl(phenyl)iodonium salts in a systematic chemoselectivity study. A new "anti-ortho effect" has been identified in the arylation of malonates. Several "dummy groups" have been found that give complete chemoselectivity in the transfer of the phenyl moiety, irrespective of the nucleophile. An aryl exchange in the diaryliodonium salts has been observed under certain arylation conditions. DFT calculations have been performed to investigate the reaction mechanism and to elucidate the origins of the observed selectivities. These results are expected to facilitate the design of chiral diaryliodonium salts and the development of catalytic arylation reactions that are based on these sustainable and metal-free reagents.
authors.affiliation: Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 106 91 Stockholm, Sweden.
authors.forename: Joel
authors.initials: J
authors.lastname: Malmgren
authors.forename: Stefano
authors.initials: S
authors.lastname: Santoro
authors.forename: Nazli
authors.initials: N
authors.lastname: Jalalian
authors.forename: Fahmi
authors.initials: F
authors.lastname: Himo
authors.forename: Berit
authors.initials: B
authors.lastname: Olofsson
keywords: DFT calculations; arylation; chemoselectivity; hypervalent compounds; ligand exchange