Cobalt-Catalyzed Methoxycarbonylation of Substituted Dichlorobenzenes as an Example of a Facile Radical Anion Nucleophilic Substitution in Chloroarenes
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 p...
| Main Authors: | , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2014-05-01
|
| Series: | Molecules |
| Subjects: | |
| Online Access: | http://www.mdpi.com/1420-3049/19/5/5876 |
| _version_ | 1828764462938587136 |
|---|---|
| author | Tatyana S. Khaibulova Irina A. Boyarskaya Evgeny Larionov Vadim P. Boyarskiy |
| author_facet | Tatyana S. Khaibulova Irina A. Boyarskaya Evgeny Larionov Vadim P. Boyarskiy |
| author_sort | Tatyana S. Khaibulova |
| collection | DOAJ |
| description | 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. |
| first_indexed | 2024-12-11T02:22:22Z |
| format | Article |
| id | doaj.art-abcc96f90d7d4439af07cc55ffbafa43 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-12-11T02:22:22Z |
| publishDate | 2014-05-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-abcc96f90d7d4439af07cc55ffbafa432022-12-22T01:24:01ZengMDPI AGMolecules1420-30492014-05-011955876589710.3390/molecules19055876molecules19055876Cobalt-Catalyzed Methoxycarbonylation of Substituted Dichlorobenzenes as an Example of a Facile Radical Anion Nucleophilic Substitution in ChloroarenesTatyana S. Khaibulova0Irina A. Boyarskaya1Evgeny Larionov2Vadim P. Boyarskiy3Chemistry Department, Saint Petersburg State University, Universitetskiy pr., 26, Staryj Petergof, 198504 St. Petersburg, RussiaChemistry Department, Saint Petersburg State University, Universitetskiy pr., 26, Staryj Petergof, 198504 St. Petersburg, RussiaDepartment of Organic Chemistry, University of Geneva, 30 Quai Ernest Ansermet, CH-1211, Geneva 4, SwitzerlandChemistry Department, Saint Petersburg State University, Universitetskiy pr., 26, Staryj Petergof, 198504 St. Petersburg, RussiaA 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.http://www.mdpi.com/1420-3049/19/5/5876cobalt-catalysed methoxycarbonylationaryl chloridessynthesis of substituted benzoic acidsradical anion nucleophilic substitutionortho-effect |
| spellingShingle | Tatyana S. Khaibulova Irina A. Boyarskaya Evgeny Larionov Vadim P. Boyarskiy Cobalt-Catalyzed Methoxycarbonylation of Substituted Dichlorobenzenes as an Example of a Facile Radical Anion Nucleophilic Substitution in Chloroarenes Molecules cobalt-catalysed methoxycarbonylation aryl chlorides synthesis of substituted benzoic acids radical anion nucleophilic substitution ortho-effect |
| title | Cobalt-Catalyzed Methoxycarbonylation of Substituted Dichlorobenzenes as an Example of a Facile Radical Anion Nucleophilic Substitution in Chloroarenes |
| title_full | Cobalt-Catalyzed Methoxycarbonylation of Substituted Dichlorobenzenes as an Example of a Facile Radical Anion Nucleophilic Substitution in Chloroarenes |
| title_fullStr | Cobalt-Catalyzed Methoxycarbonylation of Substituted Dichlorobenzenes as an Example of a Facile Radical Anion Nucleophilic Substitution in Chloroarenes |
| title_full_unstemmed | Cobalt-Catalyzed Methoxycarbonylation of Substituted Dichlorobenzenes as an Example of a Facile Radical Anion Nucleophilic Substitution in Chloroarenes |
| title_short | Cobalt-Catalyzed Methoxycarbonylation of Substituted Dichlorobenzenes as an Example of a Facile Radical Anion Nucleophilic Substitution in Chloroarenes |
| title_sort | cobalt catalyzed methoxycarbonylation of substituted dichlorobenzenes as an example of a facile radical anion nucleophilic substitution in chloroarenes |
| topic | cobalt-catalysed methoxycarbonylation aryl chlorides synthesis of substituted benzoic acids radical anion nucleophilic substitution ortho-effect |
| url | http://www.mdpi.com/1420-3049/19/5/5876 |
| work_keys_str_mv | AT tatyanaskhaibulova cobaltcatalyzedmethoxycarbonylationofsubstituteddichlorobenzenesasanexampleofafacileradicalanionnucleophilicsubstitutioninchloroarenes AT irinaaboyarskaya cobaltcatalyzedmethoxycarbonylationofsubstituteddichlorobenzenesasanexampleofafacileradicalanionnucleophilicsubstitutioninchloroarenes AT evgenylarionov cobaltcatalyzedmethoxycarbonylationofsubstituteddichlorobenzenesasanexampleofafacileradicalanionnucleophilicsubstitutioninchloroarenes AT vadimpboyarskiy cobaltcatalyzedmethoxycarbonylationofsubstituteddichlorobenzenesasanexampleofafacileradicalanionnucleophilicsubstitutioninchloroarenes |