Síntesis y estudio de aminales cíclicos y amidas derivadas
The present Ph. D. Thesis is devoted to the synthesis, NMR spectral characterization and stereochemical study of amides derived from cyclic aminals. The compounds under study were not reported in the literature, and are interesting due to their structural relationship with bioactive scaffolds and to...
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| Formato: | Tesis doctoral acceptedVersion |
| Lenguaje: | Español |
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Facultad de Farmacia y Bioquímica
2014
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| Acceso en línea: | http://repositoriouba.sisbi.uba.ar/gsdl/cgi-bin/library.cgi?a=d&c=posgraafa&cl=CL1&d=HWA_734 http://repositoriouba.sisbi.uba.ar/gsdl/collect/posgraafa/index/assoc/HWA_734.dir/734.PDF |
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| Sumario: | The present Ph. D. Thesis is devoted to the synthesis, NMR spectral characterization and stereochemical study of amides derived from cyclic aminals. The compounds under study were not reported in the literature, and are interesting due to their structural relationship with bioactive scaffolds and to their stereochemical features.\nWe have developed novel and efficient synthetic approaches to four types of compounds: N-acyl-N´-arylhexahydropyrimidines 1, N-acyl-N´-aryl-1,3-diazepanes 8, 3-acyl-1,2,3,4-tetrahydroquinazolines 17, 21, 22 with different substitution patterns and 3-acyl-1,3-oxazinanes 23, either by ring closure of aminoamides or by N-acylation of heterocyclic precursors (Scheme).\nCyclic aminal-derived amides show E/Z isomerism due to hindered rotation around the N-C(O) bond. We performed the unambiguous differential assignment of the NMR spectra of the E/Z rotamers of all the compounds and determined their relative proportions. The E/Z ratios were also investigated employing theoretical methods.\nThe rotational barriers of a group of 5 representative benzamides were determined by means of variable temperature NMR experiments and lineshape analysis. The experimental results were in accordance with data previously reported in the literature for related compounds. E/Z interconversion barriers were also studied employing DFT theoretical methods. |
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