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Ministerio de Ciencia e Innovación (Espanya)
Ministerio de Educación y Ciencia (Espanya) Generalitat de Catalunya. Agència de Gestió d’Ajuts Universitaris i de Recerca |
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Dachs Soler, Anna
Pla i Quintana, Anna Parella Coll, Teodor Solà i Puig, Miquel Roglans i Ribas, Anna |
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N-Tosyl-linked open-chain yne-ene-yne enediynes 1 and 2 and yne-yne-ene enediynes 3 and 4 have been satisfactorily synthesised. The [2+2+2] cycloaddition process catalysed by the Wilkinson catalyst [RhCl(PPh 3) 3] was tested with the above-mentioned substrates resulting in the production of high yields of the cycloadducts. Enediynes 1 and 2 gave standard [2+2+2] cycloaddition reactions whereas enediynes 3 and 4 suffered β-hydride elimination followed by reductive elimination of the Wilkinson catalyst to give cycloadducts, which are isomers of those that would be obtained by standard [2+2+2] cycloaddition reactions. The different reactivities of these two types of enediyne have been rationalised by density functional theory calculations Financial support from the Spanish MICINN (CTQ2008-05409-C02-02, CTQ2008-03077, CTQ2011-23156, CTQ2011-23121 and CTQ2009-08328) and the Catalan DIUE of the Generalitat de Catalunya (2009SGR637) is acknowledged. A. D. thanks the Spanish MEC for a doctoral fellowship. Support for the research of M. S. was received through the ICREA Academia 2009 prize for excellence in research funded by the DIUE |
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http://hdl.handle.net/2072/296593 | |
eng | |
Wiley-VCH Verlag | |
Tots els drets reservats | |
Reaccions d’addició
Addition reactions Funcional de densitat, Teoria del Density functionals Mecanismes de reacció (QuÃmica) Reaction mechanisms (Chemistry) Rodi Rhodium Ciclització (QuÃmica) Ring formation (Chemistry) |
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Intramolecular [2+2+2] cycloaddition reactions of Yne-ene-yne and Yne-yne-ene enediynes catalysed by Rh I: Experimental and theoretical mechanistic studies | |
info:eu-repo/semantics/article | |
Recercat |