Aromatic Osmacyclopropenefuran Bicycles and Their Relevance for the Metal‐Mediated Hydration of Functionalized Allenes |
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| Authors: | Dr. María Batuecas Dr. Ruth Castro‐Rodrigo Prof. Dr. Miguel A. Esteruelas Dr. Cristina García‐Yebra Prof. Dr. Ana M. López Dr. Enrique Oñate |
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| Affiliation: | Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universidad de Zaragoza-CSIC, Zaragoza, Spain |
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| Abstract: | 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. |
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| Keywords: | allenes aromaticity hydration metallaheterobicycles osmium |
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