Concerted metalation deprotonation (original) (raw)
Concerted metalation-deprotonation (CMD) is a mechanistic pathway through which transition-metal catalyzed C–H activation reactions can take place. In a CMD pathway, the C–H bond of the substrate is cleaved and the new C–Metal bond forms through a single transition state. This process does not go through a metal species that is bound to the cleaved hydrogen atom. Instead, a carboxylate or carbonate base deprotonates the substrate. The first proposal of a concerted metalation deprotonation pathway was by S. Winstein and T. G. Traylor in 1955 for the acetolysis of diphenylmercury. It was found to be the lowest energy transition state in a number of computational studies, was experimentally confirmed through NMR experiments, and has been hypothesized to occur in mechanistic studies.
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| dbo:abstract | Concerted metalation-deprotonation (CMD) is a mechanistic pathway through which transition-metal catalyzed C–H activation reactions can take place. In a CMD pathway, the C–H bond of the substrate is cleaved and the new C–Metal bond forms through a single transition state. This process does not go through a metal species that is bound to the cleaved hydrogen atom. Instead, a carboxylate or carbonate base deprotonates the substrate. The first proposal of a concerted metalation deprotonation pathway was by S. Winstein and T. G. Traylor in 1955 for the acetolysis of diphenylmercury. It was found to be the lowest energy transition state in a number of computational studies, was experimentally confirmed through NMR experiments, and has been hypothesized to occur in mechanistic studies. While there are a number of different possible mechanisms for C–H activation, a CMD pathway is common for high valent, late transition metals like PdII, RhIII, IrIII, and RuII. The C–H bonds that have been found to undergo C–H activation through CMD include those that are aryl, alkyl, and alkenyl. Investigations into CMD paved the way for the development of many new C–H functionalization reactions, especially in the areas of direct arylation and alkylation by palladium and ruthenium. (en) |
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| dbo:wikiPageWikiLink | dbr:Carbonate dbr:Benzene dbr:Benzoic_acid dbr:Biphenyl dbr:Perchloric_acid dbr:Deprotonation dbr:Infrared_spectroscopy dbr:Protonation dbc:Organic_chemistry dbr:Organomercury dbr:Transition_state dbc:Organometallic_chemistry dbr:Acetic_acid dbr:Palladium(II)_acetate dbr:Carbon–hydrogen_bond_activation dbr:Carboxylate dbr:Pivalic_acid dbr:Nuclear_magnetic_resonance dbr:Oxidative_addition dbr:Strong_inference dbr:Principle_of_Microscopic_Reversibility dbr:File:CMD-3.jpg dbr:File:CMD-4.jpg dbr:File:CMD_Mech.jpg dbr:File:CMD_mechanism_Traylor_and_Winstein.png |
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| dcterms:subject | dbc:Organic_chemistry dbc:Organometallic_chemistry |
| rdfs:comment | Concerted metalation-deprotonation (CMD) is a mechanistic pathway through which transition-metal catalyzed C–H activation reactions can take place. In a CMD pathway, the C–H bond of the substrate is cleaved and the new C–Metal bond forms through a single transition state. This process does not go through a metal species that is bound to the cleaved hydrogen atom. Instead, a carboxylate or carbonate base deprotonates the substrate. The first proposal of a concerted metalation deprotonation pathway was by S. Winstein and T. G. Traylor in 1955 for the acetolysis of diphenylmercury. It was found to be the lowest energy transition state in a number of computational studies, was experimentally confirmed through NMR experiments, and has been hypothesized to occur in mechanistic studies. (en) |
| rdfs:label | Concerted metalation deprotonation (en) |
| owl:sameAs | wikidata:Concerted metalation deprotonation https://global.dbpedia.org/id/FpLDt |
| prov:wasDerivedFrom | wikipedia-en:Concerted_metalation_deprotonation?oldid=1083014540&ns=0 |
| foaf:depiction | wiki-commons:Special:FilePath/CMD-3.jpg wiki-commons:Special:FilePath/CMD-4.jpg wiki-commons:Special:FilePath/CMD_Mech.jpg wiki-commons:Special:FilePath/CMD_mechanism_Traylor_and_Winstein.png |
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| is foaf:primaryTopic of | wikipedia-en:Concerted_metalation_deprotonation |
