Chemoselectivity of cobalt-catalysed carbonylation—A reliable platform for the synthesis of fluorinated benzoic acids

Boyarskiy, Vadim P.; Fonarı, Marina S.; Khaybulova, Tatiana S.; Gdaniec, Мaria; Simonov, Yurii A.

doi:10.1016/j.jfluchem.2009.10.010

Cited by 5 publications

(2 citation statements)

References 27 publications

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“…In order to study the ortho-effect of substituents in more detail, we measured the regioselectivity of the amination for substituted dichlorobenzenes, which usually are more reactive in couplings than monochlorobenzenes. 19,20 This approach to orthoeffect studying was developed by us early previously for cobalt-catalyzed methoxycarbonylation of aryl halides 19,20 and for palladium-catalyzed cross-couplings. 21 The essence is to make a difference between the chlorine atoms due to an additional substituent into the dichlorobenzene molecule.…”

Section: Scheme 1mentioning

confidence: 99%

Copper-catalyzed C–N bond cross-coupling of aryl halides and amines in water in the presence of ligand derived from oxalyl dihydrazide: scope and limitation

et al. 2015

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Section: Scheme 1mentioning

confidence: 99%

Copper-catalyzed C–N bond cross-coupling of aryl halides and amines in water in the presence of ligand derived from oxalyl dihydrazide: scope and limitation

et al. 2015

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“…The methoxycarbonylation of only a few dichlorobenzenes has been described under these conditions [37]. At the same time, cobalt-catalysed methoxycarbonylation gives a good opportunity to study the principles of the radical anion processes in chloroarenes.…”

Section: Introductionmentioning

confidence: 99%

Cobalt-Catalyzed Methoxycarbonylation of Substituted Dichlorobenzenes as an Example of a Facile Radical Anion Nucleophilic Substitution in Chloroarenes

et al. 2014

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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, P CO = 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.

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ChemInform Abstract: Chemoselectivity of Cobalt‐Catalyzed Carbonylation — A Reliable Platform for the Synthesis of Fluorinated Benzoic Acids.

et al. 2010

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Acids. -Methoxycarbonylation of polyhalogenated benzene (I) shows that fluorine substitution is not observed. Carbonylation of trichlorobenzene (VI), carried out under the same conditions, occurs in position 2 leading to methyldichlorobenzoate (VII) as the major product. Thus the selectivity of the carbonylation process of (I) is predominantly determined by the nature of halogen rather than by the relative positions of the substituents at the aromatic ring. Since the fluorine atom in (I) remains intact this clearly indicates the anion-radical activation character of aryl halides by a cobalt catalyst. -(BOYARSKIY, V. P.; FONARI*, M. S.; KHAYBULOVA, T. S.; GDANIEC, M.; SIMONOV, Y. A.; J. Fluorine Chem. 131 (2010) 1, 81-85,

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Chemoselectivity of cobalt-catalysed carbonylation—A reliable platform for the synthesis of fluorinated benzoic acids

Cited by 5 publications

References 27 publications

Copper-catalyzed C–N bond cross-coupling of aryl halides and amines in water in the presence of ligand derived from oxalyl dihydrazide: scope and limitation

Copper-catalyzed C–N bond cross-coupling of aryl halides and amines in water in the presence of ligand derived from oxalyl dihydrazide: scope and limitation

Cobalt-Catalyzed Methoxycarbonylation of Substituted Dichlorobenzenes as an Example of a Facile Radical Anion Nucleophilic Substitution in Chloroarenes

ChemInform Abstract: Chemoselectivity of Cobalt‐Catalyzed Carbonylation — A Reliable Platform for the Synthesis of Fluorinated Benzoic Acids.

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