Mild Oxidation of C−C Bonds of Benzoiridacycles
| Autor: | Rosa Padilla, Margarita Paneque, Joaquín Tamariz, Héctor Pacheco-Cuvas, José G. Alvarado-Rodríguez, Verónica Salazar, Florencia Vattier |
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| Rok vydání: | 2010 |
| Předmět: |
Ketone
Acetylenedicarboxylate Substituent chemistry.chemical_element Iridium Oxygen Medicinal chemistry Inorganic Chemistry Metal chemistry.chemical_compound Metallacycles Oxidation Organic chemistry Molecule Physical and Theoretical Chemistry Boron chemistry.chemical_classification Chemistry Organic Chemistry NMR visual_art visual_art.visual_art_medium Molecular structure |
| Zdroj: | Digital.CSIC. Repositorio Institucional del CSIC instname |
| ISSN: | 1520-6041 0276-7333 |
| DOI: | 10.1021/om100196h |
| Popis: | 4 páginas, 1 figura, 2 esquemas. We describe herein the formation of two metallacyclic derivatives, 4b and 5b, which contain a coordinated ketone functionality (from an α-keto ester metallacyclic substituent). An iridafuran, 6, that results from the reaction of TpMe2Ir(Ph)2(N2) (TpMe2 = hydrotris(3,5-dimethylpyrazolyl)borate) with di-tert-butyl acetylenedicarboxylate (DTAD) and oxygen is also reported. Our results reveal that the reactions proceed through iridacycle intermediates (detected by NMR) resulting formally from the coupling of one (in the case of 6) or two (for 4b and 5b) molecules of DTAD, with the metal unit “TpMe2Ir(C6H4)” derived from the iridium precursor. These intermediates experience very mild and selective oxidation by air to incorporate one (4b and 5b) or three (6) oxygen atoms in the final oxidation products. Financial support from the CONACYT (Grants 025424 and 84453), from the Junta de Andalucía (Group FQM-119 and Project P09-FQM-4832), and from the Spanish Ministry of Science (MICINN, Projects CTQ2007-62814 and Consolider Ingenio-2010 CSD2007-00006) (FEDER support). |
| Databáze: | OpenAIRE |
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