Quaternary chiral β 2,2-amino acids with pyridinium and imidazolium substituents
The reactions of cyclic sulfamidates as electrophiles with a variety of nitrogen-containing aromatic heterocycle nucleophiles, such as pyridines, N-alkylimidazoles and N-methylbenzimidazol, was explored. In all cases, although the nucleophilic substitution reactions occurred on quaternary centres, e...
| Autores: | , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2012 |
| País: | España |
| Institución: | Universidad de La Rioja (UR) |
| Repositorio: | RIUR. Repositorio Institucional de la Universidad de La Rioja |
| OAI Identifier: | oai:portal.dialnet.es:doc/5bbc68dbb750603269e810d1 |
| Acceso en línea: | https://investigacion.unirioja.es/documentos/5bbc68dbb750603269e810d1 |
| Access Level: | acceso abierto |
| Palabra clave: | amino acids conformational analysis heterocycles imidazoles molecular dynamics nucleophilic substitution |
| Sumario: | The reactions of cyclic sulfamidates as electrophiles with a variety of nitrogen-containing aromatic heterocycle nucleophiles, such as pyridines, N-alkylimidazoles and N-methylbenzimidazol, was explored. In all cases, although the nucleophilic substitution reactions occurred on quaternary centres, elimination products were not detected. The inversion of configuration at this quaternary centre was determined by X-ray diffraction analysis and the enantiomeric excess of the reactions was checked by chiral HPLC. This synthetic approach allowed us to obtain a new family of chiral charged β2,2-amino acids, including a new bisamino acid that incorporates an imidazolium salt as a cross-linker. In this context, the treatment of these chiral imidazolium salts with Ag2O opens the way to new chiral N-heterocyclic carbenes, which are important substrates in the fields of organometallic and organocatalytic chemistry. Additionally, we have done a thorough conformational analysis of these β-amino acid derivatives, both in the solid state and in solution. The most important conformational feature of these acyclic systems is the rigidity of the N-CH2-C- N+ dihedral angle, which is essentially due to the gauche effect. Chiral β2,2-amino acids: Nitrogen-containing aromatic heterocycles were used as nucleophiles in the opening reaction of cyclic sulfamidates to obtain a new family of chiral β2,2-amino acids with pyridinium and imidazolium substituents, which show a rigid N-CH 2-C-N+ dihedral angle due to the gauche effect. These chiral imidazolium derivatives open the way to the synthesis of new chiral N-heterocyclic carbenes. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. |
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