{"id":96821,"date":"2018-03-11T10:17:08","date_gmt":"2018-03-11T10:17:08","guid":{"rendered":"https:\/\/www.deberes.net\/tesis\/sin-categoria\/organocatalisis-asimetrica-mediante-activacion-via-iminio-en-reacciones-de-adicion-conjugada\/"},"modified":"2018-03-11T10:17:08","modified_gmt":"2018-03-11T10:17:08","slug":"organocatalisis-asimetrica-mediante-activacion-via-iminio-en-reacciones-de-adicion-conjugada","status":"publish","type":"post","link":"https:\/\/www.deberes.net\/tesis\/compuestos-heterociclicos\/organocatalisis-asimetrica-mediante-activacion-via-iminio-en-reacciones-de-adicion-conjugada\/","title":{"rendered":"Organocatalisis asimetrica mediante activacion via iminio en reacciones de adicion conjugada"},"content":{"rendered":"<h2>Tesis doctoral de <strong> Uxue Uria Pujana <\/strong><\/h2>\n<p>En el trabajo de investigaci\u00f3n que se recoge en la presente memoria se han estudiado una serie de estrategias que tienen como finalidad la s\u00edntesis asim\u00e9trica de compuestos de inter\u00e9s con elevado rendimiento y control estereoqu\u00edmico. \u00e9stas est\u00e1n enmarcadas en el uso de organocatalizadores a modo de elementos estereocontroladores donde el tipo de activaci\u00f3n del sustrato de partida se basa en la formaci\u00f3n de iones iminio quirales. En este sentido, se ha demostrado la viabilidad de esta activaci\u00f3n organocatal\u00edtica tanto en reacciones aza-michael como en ciclopropanaciones mediante un proceso en cascada michael\/a- alquilaci\u00f3n. as\u00ed, en primer lugar se ha estudiado la reacci\u00f3n aza-michael entre distintos heterociclos nitrogenados y aldeh\u00eddos a,b-insaturados diferentemente sustituidos, comprobando que tanto el catalizador empleado, la temperatura de la transformaci\u00f3n como la reducci\u00f3n in situ del aducto aza-michael son aspectos claves para controlar la estereoqu\u00edmica del proceso. La versatilidad sint\u00e9tica de los aductos obtenidos permiti\u00f3 llevar a cabo su posterior derivatizaci\u00f3n, pudi\u00e9ndose destacar la s\u00edntesis de oxaziniminas, formamidinas, ureas e isoureas de alto valor a\u00f1adido. Adem\u00e1s, mediante un estudio mecan\u00edstico basado en datos computacionales y experimentales, se ha propuesto un modelo cualitativo que permite explicar la estereoqu\u00edmica inusual obtenida en los productos aza-michael. en cuanto a la reacci\u00f3n de ciclopropanaci\u00f3n, se han estudiado dos rutas sint\u00e9ticas diferentes, observando que mientras la cicloadici\u00f3n 1,3-dipolar entre diazoalcanos y aldeh\u00eddos a,b-insaturados no resulta factible, el proceso en cascada michael\/a-alquilaci\u00f3n de aldeh\u00eddos \u00c2\u00bf,\u00edY-insaturados con bromomalonato de dietilo proporciona los aductos polisustituidos funcionalizados objetivo con resultados satisfactorios empleando agua como \u00fanico disolvente y sin la necesidad de a\u00f1adir ning\u00fan tipo de base externa, procedimiento habitual en transformaciones similares.<\/p>\n<p>&nbsp;<\/p>\n<h3>Datos acad\u00e9micos de la tesis doctoral \u00ab<strong>Organocatalisis asimetrica mediante activacion via iminio en reacciones de adicion conjugada<\/strong>\u00ab<\/h3>\n<ul>\n<li><strong>T\u00edtulo de la tesis:<\/strong>\u00a0 Organocatalisis asimetrica mediante activacion via iminio en reacciones de adicion conjugada <\/li>\n<li><strong>Autor:<\/strong>\u00a0 Uxue Uria Pujana <\/li>\n<li><strong>Universidad:<\/strong>\u00a0 Pa\u00eds vasco\/euskal herriko unibertsitatea<\/li>\n<li><strong>Fecha de lectura de la tesis:<\/strong>\u00a0 27\/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>Jos\u00e9 Luis Vicario Hernando<\/li>\n<\/ul>\n<\/li>\n<li><strong>Tribunal<\/strong>\n<ul>\n<li>Presidente del tribunal: santos Fustero lardi\u00e9s <\/li>\n<li>Jos\u00e9 Mar\u00eda Lassaletta simon (vocal)<\/li>\n<li>Rafael Pedrosa saez (vocal)<\/li>\n<li>pedro Merino filella (vocal)<\/li>\n<\/ul>\n<\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n","protected":false},"excerpt":{"rendered":"<p>Tesis doctoral de Uxue Uria Pujana En el trabajo de investigaci\u00f3n que se recoge en la presente memoria se han [&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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