Understanding the regioselectivity of Michael addition reactions to asymmetric divinylic compounds
| Autor: | Anselmo del Prado, Serena Molina, Cristina Monterde, Alberto Gallardo, Rodrigo Navarro, Helmut Reinecke, Felipe Reviriego, Mónica Pérez-Perrino |
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| Přispěvatelé: | Ministerio de Economía, Industria y Competitividad (España) |
| Rok vydání: | 2017 |
| Předmět: |
Acrylate
General Chemical Engineering Regioselectivity 02 engineering and technology General Chemistry 010402 general chemistry 021001 nanoscience & nanotechnology Methacrylate QD Chemistry 01 natural sciences Combinatorial chemistry TP Chemical technology 0104 chemical sciences chemistry.chemical_compound Monomer chemistry Nucleophile Michael reaction Reactivity (chemistry) Chemoselectivity 0210 nano-technology |
| Zdroj: | Digital.CSIC. Repositorio Institucional del CSIC instname BASE-Bielefeld Academic Search Engine |
| Popis: | In the present paper, we describe the synthesis of novel monomers prepared by regioselective Michael addition to asymmetric divinylic compounds. This chemoselectivity was experimentally studied employing different reaction conditions and theoretically calculated using chemical global and local descriptors. The global reactivity data show that incoming nucleophilic secondary amines preferentially attack the acrylic derived units acrylate and acrylamide, while deactivated methacrylate and N-vinyl-pyrrolidone require harder reaction conditions, which leads to the formation of by-products. Moreover, it is demonstrated that the presence of two vinyl units within a studied divinylic agent leads to a significant increase in its global reactivity parameters. Besides, the local reactivity parameters of asymmetric divinyl compounds show a preference for an attack at the C of activated units compared to the C center of deactivated units. Based on these results, asymmetric divinyl compounds are very interesting starting materials for the preparation of new functionalized monomers. The authors gratefully acknowledge financial support from the Consejo Superior de Investigaciones Científicas (CSIC). Equally, this work was financially supported by the Ministerio de Economía y Competitividad (MINECO) through MAT2013-42957-R. R. N. is grateful for a contract of the Postdoctoral Formation program from the Ministerio de Economía y Competitividad |
| Databáze: | OpenAIRE |
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