{"id":96452,"date":"2009-07-10T00:00:00","date_gmt":"2009-07-10T00:00:00","guid":{"rendered":"https:\/\/www.deberes.net\/tesis\/sin-categoria\/sa%c2%adntesis-enantioselectiva-de-piperidinas-indolo23-a-y-benzoaquinolizidinas-a-partir-de-oxazolopiperidonas-quirales-sa%c2%adntesis-formal-de-alcaloides-indolicos\/"},"modified":"2009-07-10T00:00:00","modified_gmt":"2009-07-10T00:00:00","slug":"sa%c2%adntesis-enantioselectiva-de-piperidinas-indolo23-a-y-benzoaquinolizidinas-a-partir-de-oxazolopiperidonas-quirales-sa%c2%adntesis-formal-de-alcaloides-indolicos","status":"publish","type":"post","link":"https:\/\/www.deberes.net\/tesis\/quimica-organica\/sa%c2%adntesis-enantioselectiva-de-piperidinas-indolo23-a-y-benzoaquinolizidinas-a-partir-de-oxazolopiperidonas-quirales-sa%c2%adntesis-formal-de-alcaloides-indolicos\/","title":{"rendered":"S\u00edntesis enantioselectiva de piperidinas, indolo[2,3-a]- y benzo[a]quinolizidinas a partir de oxazolopiperidonas quirales. s\u00edntesis formal de alcaloides ind\u00f3licos"},"content":{"rendered":"<h2>Tesis doctoral de <strong> Mar\u00eda  Arantzazu G\u00f3mez Esqu\u00e9 <\/strong><\/h2>\n<p>Los procedimientos estereoselectivos destinados a la preparaci\u00f3n de derivados quirales de la piperidina en forma enantiopura han suscitado elevado inter\u00e9s debido a la ubiquidad de este heterociclo entre los alcaloides (m\u00e1s de la mitad de los alcaloides conocidos lo contienen) y numerosos f\u00e1rmacos. en la presente tesis doctoral se han desarrollado m\u00e9todos para la introducci\u00f3n de manera estereoselectiva de sustituyentes en lactamas bic\u00edclicas derivadas de fenilglicinol sustitu\u00eddas mediante reacciones de alquilaci\u00f3n y \u00c2\u00bf-amidoalquilaci\u00f3n. Las reacciones de alquilaci\u00f3n de oxazolopiperidinas derivadas del fenilglicinol permiten la introducci\u00f3n estereoselectiva de una amplia variedad de sustituyentes (alquilo, bencilo, alilo, tert-butoxicarbonilmetilo) en la posici\u00f3n alfa-del carbonilo lact\u00e1mico. Posteriores manipulaciones sint\u00e9ticas conducen a piperidinas enantiopuras con diversos patrones de sustituci\u00f3n como por ejemplo piperidinas cis-2,3,5-trisustituidas y trans-2,5-disustituidas.  por otro lado, tambi\u00e9n se han estudiado las diferentes v\u00edas de acceso a derivados de benzo[a]- e indolo[2,3-a]quinolizidinas a partir de lactamas bic\u00edclicas quirales derivadas de (s)-3,4-dimetoxifenilalaninol y (s)-triptofanol, \u00fanicamente en dos etapas sint\u00e9ticas. En este caso los aminoalcoholes (s)-triptofanol y (s)-3,4-dimetoxifenilalaninol no s\u00f3lo constituyen la fuente de quiralidad actuando como inductores quirales en reacciones de ciclocondensaci\u00f3n altamente estereoselectivas, sino que adem\u00e1s forman parte de la estructura de los compuestos objetivo. Finalmente, el acceso a los derivados indolo[2,3-a]- y benzo[a]quinolizid\u00ednicos, se ha logrado mediante el empleo de reacciones de \u00c2\u00bf-amidoalquilaci\u00f3n intramolecular del anillo arom\u00e1tico de estas lactamas, a partir de las correspondientes sales de n-aciliminio generadas en medio \u00e1cido.  en este contexto, las reacciones de ciclaci\u00f3n mediante la manipulaci\u00f3n del carbonilo lact\u00e1mico de las lactamas bic\u00edclicas con estructura de oxazolopiperidona derivadas de (s)-triptofanol han permitido acceder al fragmento de 3-etilindolo[2,3-a]quinolizidina presente en un gran n\u00famero de alcaloides ind\u00f3licos. Con objeto de ilustrar la utilidad sint\u00e9tica de la metodolog\u00eda desarrollada, se ha llevado a cabo la s\u00edntesis formal total enantioselectiva de (+)-dihidrocorinante\u00edna y (-)-dihidrocorinanteol y de los alcaloides oxiind\u00f3licos (-)-rincofil\u00edna y (+)-isorincofil\u00edna.<\/p>\n<p>&nbsp;<\/p>\n<h3>Datos acad\u00e9micos de la tesis doctoral \u00ab<strong>S\u00edntesis enantioselectiva de piperidinas, indolo[2,3-a]- y benzo[a]quinolizidinas a partir de oxazolopiperidonas quirales. s\u00edntesis formal de alcaloides ind\u00f3licos<\/strong>\u00ab<\/h3>\n<ul>\n<li><strong>T\u00edtulo de la tesis:<\/strong>\u00a0 S\u00edntesis enantioselectiva de piperidinas, indolo[2,3-a]- y benzo[a]quinolizidinas a partir de oxazolopiperidonas quirales. s\u00edntesis formal de alcaloides ind\u00f3licos <\/li>\n<li><strong>Autor:<\/strong>\u00a0 Mar\u00eda  Arantzazu G\u00f3mez Esqu\u00e9 <\/li>\n<li><strong>Universidad:<\/strong>\u00a0 Barcelona<\/li>\n<li><strong>Fecha de lectura de la tesis:<\/strong>\u00a0 07\/10\/2009<\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n<h3>Direcci\u00f3n y tribunal<\/h3>\n<ul>\n<li><strong>Director de la tesis<\/strong>\n<ul>\n<li>Mercedes Amat Tus\u00f3n<\/li>\n<\/ul>\n<\/li>\n<li><strong>Tribunal<\/strong>\n<ul>\n<li>Presidente del tribunal: Jes\u00fas Jim\u00e9nez-barbero <\/li>\n<li>pedro Miguel Carda us\u00f3 (vocal)<\/li>\n<li>  (vocal)<\/li>\n<li>  (vocal)<\/li>\n<\/ul>\n<\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n","protected":false},"excerpt":{"rendered":"<p>Tesis doctoral de Mar\u00eda Arantzazu G\u00f3mez Esqu\u00e9 Los procedimientos estereoselectivos destinados a la preparaci\u00f3n de derivados quirales de la piperidina [&hellip;]<\/p>\n","protected":false},"author":1,"featured_media":0,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"site-sidebar-layout":"default","site-content-layout":"","ast-site-content-layout":"","site-content-style":"default","site-sidebar-style":"default","ast-global-header-display":"","ast-banner-title-visibility":"","ast-main-header-display":"","ast-hfb-above-header-display":"","ast-hfb-below-header-display":"","ast-hfb-mobile-header-display":"","site-post-title":"","ast-breadcrumbs-content":"","ast-featured-img":"","footer-sml-layout":"","theme-transparent-header-meta":"","adv-header-id-meta":"","stick-header-meta":"","header-above-stick-meta":"","header-main-stick-meta":"","header-below-stick-meta":"","astra-migrate-meta-layouts":"default","ast-page-background-enabled":"default","ast-page-background-meta":{"desktop":{"background-color":"var(--ast-global-color-4)","background-image":"","background-repeat":"repeat","background-position":"center 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