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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Autor principal:	Bisceglia, Juan Ángel
Otros Autores:	Orelli, Liliana Raquel
Formato:	Tesis doctoral acceptedVersion
Lenguaje:	Español
Publicado:	Facultad de Farmacia y Bioquímica 2014
Materias:	Aminales cíclicos Amidas RMN Estereoquímica Modelado molecular Química orgánica
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
Aporte de:	Repositorio Digital de la Universidad de Buenos Aires (UBA) de Universidad de Buenos Aires

id	I28-R145-HWA_734
record_format	dspace
spelling	I28-R145-HWA_7342019-09-25 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. Fil: Bisceglia, Juan Ángel. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; Argentina Facultad de Farmacia y Bioquímica Orelli, Liliana Raquel Bisceglia, Juan Ángel 2014-05-23 En el presente Trabajo de Tesis se aborda la síntesis, caracterización y estudio estereoquímico de amidas derivadas de aminales cíclicos. Estos compuestos presentan escasos antecedentes en la bibliografía, y resultan de interés tanto por su relación estructural con compuestos bioactivos como por sus características estereoquímicas.\nSe desarrollaron síntesis novedosas y eficientes de cuatro familias de compuestos: N-acil-N´-arilhexahidropirimidinas, N-acil-N´-aril-1,3-diazepanos, 3-acil-1,2,3,4-tetrahidroquinazolinas con distintos patrones de sustitución y 3-acil-1,3-oxazinanos mediante dos rutas complementarias: ciclocondensación de aminoamidas o acilación de precursores heterocíclicos (Esquema).\nLas amidas derivadas de aminales cíclicos presentan estereoisomería E/Z por restricción a la libre rotación en torno al enlace N-C(O). En todos los casos se asignaron inequívocamente los espectros de RMN de los rotámeros E/Z y se determinó su proporción relativa. Los resultados obtenidos fueron interpretados por métodos teóricos.\nMediante experimentos de RMN a temperatura variable y lineshape analysis se determinaron las barreras rotacionales de un grupo de benzamidas representativas de las variaciones estructurales planteadas en este trabajo. Los valores obtenidos para la energía de activación resultaron concordantes con los datos disponibles en la bibliografía. Las barreras también fueron investigadas por métodos de química computacional. application/pdf Aguirre, José Palermo, Jorge Segall, Adriana Aminales cíclicos Amidas RMN Estereoquímica Modelado molecular spa Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by-nc-nd/2.5/ar/ Química orgánica Síntesis y estudio de aminales cíclicos y amidas derivadas info:eu-repo/semantics/doctoralThesis info:ar-repo/semantics/tesis doctoral info:eu-repo/semantics/acceptedVersion 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
institution	Universidad de Buenos Aires
institution_str	I-28
repository_str	R-145
collection	Repositorio Digital de la Universidad de Buenos Aires (UBA)
language	Español
orig_language_str_mv	spa
topic	Aminales cíclicos Amidas RMN Estereoquímica Modelado molecular Química orgánica
spellingShingle	Aminales cíclicos Amidas RMN Estereoquímica Modelado molecular Química orgánica Bisceglia, Juan Ángel Síntesis y estudio de aminales cíclicos y amidas derivadas
topic_facet	Aminales cíclicos Amidas RMN Estereoquímica Modelado molecular Química orgánica
description	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.
author2	Orelli, Liliana Raquel
author_facet	Orelli, Liliana Raquel Bisceglia, Juan Ángel
format	Tesis doctoral Tesis doctoral acceptedVersion
author	Bisceglia, Juan Ángel
author_sort	Bisceglia, Juan Ángel
title	Síntesis y estudio de aminales cíclicos y amidas derivadas
title_short	Síntesis y estudio de aminales cíclicos y amidas derivadas
title_full	Síntesis y estudio de aminales cíclicos y amidas derivadas
title_fullStr	Síntesis y estudio de aminales cíclicos y amidas derivadas
title_full_unstemmed	Síntesis y estudio de aminales cíclicos y amidas derivadas
title_sort	síntesis y estudio de aminales cíclicos y amidas derivadas
publisher	Facultad de Farmacia y Bioquímica
publishDate	2014
url	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
work_keys_str_mv	AT biscegliajuanangel sintesisyestudiodeaminalesciclicosyamidasderivadas
_version_	1766017568250789888

Síntesis y estudio de aminales cíclicos y amidas derivadas

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