title: Cobalt-catalyzed methoxycarbonylation of substituted dichlorobenzenes as an example of a facile radical anion nucleophilic substitution in chloroarenes.
abstract: A thorough mechanistic study on cobalt-catalysed direct methoxycarbonylation reactions of chlorobenzenes in the presence of methyl oxirane on a wide range of substrates, including poly- and monochloro derivatives with multiple substituents, is reported. The results demonstrate that the reaction is potentially useful as it proceeds under very mild conditions (t = 62 °C, PCO = 1 bar) and converts aryl chlorides to far more valuable products (especially ortho-substituted benzoic acids and esters) in high yields. This transformation also offers another opportunity for the utilization of environmentally harmful polychlorinated benzenes and biphenyls (PCBs). This study is the first to discover an unexpected universal positive ortho-effect: the proximity of any substituent (including Me, Ph, and MeO groups and halogen atoms) to the reaction centre accelerates the methoxycarbonylation in chlorobenzenes. The effect of the ortho-substituents is discussed in detail and explained in terms of a radical anion reaction mechanism. The advantages of the methoxycarbonylation as a model for the mechanistic study of radical anion reactions are also illustrated.
authors.affiliation: Chemistry Department, Saint Petersburg State University, Universitetskiy pr., 26, Staryj Petergof, 198504 St. Petersburg, Russia.
authors.forename: Tatyana S
authors.initials: TS
authors.lastname: Khaibulova
authors.affiliation: Chemistry Department, Saint Petersburg State University, Universitetskiy pr., 26, Staryj Petergof, 198504 St. Petersburg, Russia.
authors.forename: Irina A
authors.initials: IA
authors.lastname: Boyarskaya
authors.affiliation: Department of Organic Chemistry, University of Geneva, 30 Quai Ernest Ansermet, CH-1211, Geneva 4, Switzerland.
authors.forename: Evgeny
authors.initials: E
authors.lastname: Larionov
authors.affiliation: Chemistry Department, Saint Petersburg State University, Universitetskiy pr., 26, Staryj Petergof, 198504 St. Petersburg, Russia. vadim.boyarskiy@chem.spbu.ru.
authors.forename: Vadim P
authors.initials: VP
authors.lastname: Boyarskiy
mesh_terms: D000838:Anions / Q000737:chemistry; D001554:Benzene / Q000737:chemistry; D002384:Catalysis; D002722:Chlorobenzenes / Q000737:chemistry*; D003035:Cobalt / Q000737:chemistry; D005609:Free Radicals / Q000737:chemistry*; D006219:Halogens / Q000737:chemistry; D055601:Organic Chemistry Phenomena
chemical_list: D000838:Anions; D002722:Chlorobenzenes; D005609:Free Radicals; D006219:Halogens; D003035:Cobalt; D001554:Benzene