Aromatic Osmacyclopropenefuran Bicycles and Their Relevance for the Metal-Mediated Hydration of Functionalized Allenes
| Autor: | Ruth Castro-Rodrigo, Enrique Oñate, Ana M. López, Miguel A. Esteruelas, Cristina García-Yebra, María Batuecas |
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| Přispěvatelé: | Diputación General de Aragón, Ministerio de Economía y Competitividad (España), European Commission |
| Rok vydání: | 2016 |
| Předmět: |
Stereochemistry
010405 organic chemistry Aromaticity Allene Regioselectivity chemistry.chemical_element Hydration General Chemistry General Medicine 010402 general chemistry Osmium 01 natural sciences Catalysis 0104 chemical sciences Metal chemistry.chemical_compound chemistry Metallaheterobicycles visual_art visual_art.visual_art_medium Allenes |
| Zdroj: | Digital.CSIC. Repositorio Institucional del CSIC instname Zaguán. Repositorio Digital de la Universidad de Zaragoza |
| ISSN: | 1521-3773 |
| Popis: | In memory of José Barluenga (1940–2016). The aromatic osmacyclopropenefuran bicycles [OsTp{κ3-C1,C2,O-(C1H2C2CHC(OEt)O)}(PiPr3)]BF4 (Tp=hydridotris(1-pyrazolyl)borate) and [OsH{κ3-C1,C2,O-(C1H2C2CHC(OEt)O)}(CO)(PiPr3)2]BF4, with the metal fragment in a common vertex between the fused three- and five-membered rings, have been prepared via the π-allene intermediates [OsTp(η2-CH2=CCHCO2Et)(OCMe2)(PiPr3)]BF4 and [OsH(η2-CH2=CCHCO2Et)(CO)(OH2)(PiPr3)2]BF4, and their aromaticity analyzed by DFT calculations. The bicycle containing the [OsH(CO)(PiPr3)2]+ metal fragment is a key intermediate in the [OsH(CO)(OH2)2(PiPr3)2]BF4-catalyzed regioselective anti-Markovnikov hydration of ethyl buta-2,3-dienoate to ethyl 4-hydroxycrotonate. Financial support from the MINECO of Spain (Projects CTQ2014-52799-P and CTQ2014-51912-REDC), the Diputación General de Aragón (E-35), FEDER, and the European Social Fund is acknowledged. |
| Databáze: | OpenAIRE |
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