Transition metal-catalysed [2+2+2] cycloaddition reactions. Methodology and mechanism
The transition-metal catalysed [2+2+2] cycloaddition reaction is a highly efficient synthetic tool that allows six-membered polysubstituted carbo- and heterocyclic derivatives to be obtained in an atom economy process. This doctoral thesis is based on methodological and mechanistic studies of the rh...
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| Tipo de recurso: | tesis doctoral |
| Estado: | Versión publicada |
| Fecha de publicación: | 2014 |
| País: | España |
| Institución: | CBUC, CESCA |
| Repositorio: | TDR. Tesis Doctorales en Red |
| OAI Identifier: | oai:www.tdx.cat:10803/145035 |
| Acceso en línea: | http://hdl.handle.net/10803/145035 |
| Access Level: | acceso abierto |
| Palabra clave: | Rhodium Rodi Rodio Cycloaddition Cicloaddició Cicloadición Catalysts Catalitzadors Catalizadores ESI-MS Hemilabile ligands Chiral Baylis-Hillman 547 |
| Sumario: | The transition-metal catalysed [2+2+2] cycloaddition reaction is a highly efficient synthetic tool that allows six-membered polysubstituted carbo- and heterocyclic derivatives to be obtained in an atom economy process. This doctoral thesis is based on methodological and mechanistic studies of the rhodium(I)-catalysed [2+2+2] cycloaddition reaction. In particular, the use of hemilabile S-stereogenic and P-stereogenic ligands for the rhodium-catalysed [2+2+2] cycloaddition is described. The activity of these new catalytic systems is evaluated in the cycloaddition of three alkynes and in the enantioselective cycloaddition of enediynes to obtain chiral cyclohexa-1,3-dienes. Moreover, the participation of Baylis-Hillman adducts as alkene moieties for the partially intramolecular [2+2+2] cycloaddition is described for the synthesis of a set of enantioenriched bicyclic cyclohexadienes featuring a quaternary stereogenic centre. Finally, the mechanistic study of the [2+2+2] cycloaddition of alkynes by electrospray ionization mass spectrometry and DFT calculations is performed. |
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