{"id":55392,"date":"2006-08-11T00:00:00","date_gmt":"2006-08-11T00:00:00","guid":{"rendered":"https:\/\/www.deberes.net\/tesis\/sin-categoria\/aplicaciones-sinteticas-de-los-aductos-de-pauson-khand-del-norbomadieno-aproximacion-a-la-sa%c2%adntesis-de-prostaglandinas-y-fitoprostanos\/"},"modified":"2006-08-11T00:00:00","modified_gmt":"2006-08-11T00:00:00","slug":"aplicaciones-sinteticas-de-los-aductos-de-pauson-khand-del-norbomadieno-aproximacion-a-la-sa%c2%adntesis-de-prostaglandinas-y-fitoprostanos","status":"publish","type":"post","link":"https:\/\/www.deberes.net\/tesis\/barcelona\/aplicaciones-sinteticas-de-los-aductos-de-pauson-khand-del-norbomadieno-aproximacion-a-la-sa%c2%adntesis-de-prostaglandinas-y-fitoprostanos\/","title":{"rendered":"Aplicaciones sint\u00e9ticas de los aductos de pauson-khand del norbomadieno. aproximaci\u00f3n a la s\u00edntesis de prostaglandinas y fitoprostanos"},"content":{"rendered":"<h2>Tesis doctoral de <strong> Agust\u00ed Lled\u00f3 Ponsati <\/strong><\/h2>\n<p>Se han optimizado metodolog\u00edas para la obtenci\u00f3n de aductos de pauson-khand del norbornadieno y acetilenos terminales, bien sea en forma enantiopura mediante reacciones de pauson-khand estequiom\u00e9tricas o bien forma rac\u00e9mica cuando protocolos catal\u00edticos que simplifican la purificaci\u00f3n de los productos. En estas condiciones se observa la formaci\u00f3n del diastererois\u00f3mero endo no deseado en proporciones apreciables. esto se minimiza dr\u00e1sticamente sustituyendo un ligando co por trifenilfosfina en el catalizador de cobalto. El aducto de pauson-khand del norbonadieno y el trimetilsililacetileno (1) \u00f3pticamente puro se ha transformado en lso desoxifitoprostanos dppj1-l i ll, confirmando as\u00ed por vez primera su estereoqu\u00edmica absoluta y relativa. De forma preliminar se han ensayado varios auxiliares quirales en la reacci\u00f3n de pauson -khand catal\u00edtica y enantioselectiva sin haber llegado hasta el momento a buenos excesos enantiom\u00e9ricos.     se han estudiado las transformaciones sint\u00e9ticas sobre el aducto de pauson-khand (1) rac\u00e9mico, centr\u00e1ndose en reacciones de adici\u00f3n conjugada y desililaci\u00f3n. En primer lugar se han preparado las correspondientes cetonas beta-sustituidas con diversos sustituyentes alif\u00e1ticos por adici\u00f3n conjugada bien de dialquilcupratos de litio o bien de reactivos de grignard en presencia de cantidades catal\u00edticas de cu(i). Sobre esos sustratos se ha desarrollado una secuencia de metilenaci\u00f3n\/adici\u00f3n conjugada para introducir sustituyentes en posici\u00f3n alfa al carbonilo. Por adici\u00f3n conjugada de sintones d1 sobre el aducto 1 se han preparado 1,4-hidroxicetonas y 1,4-oxoaldehidos. Para ello se ha utilizado el ani\u00f3n cianuro como equivalente sint\u00e9tico de un aldehido y tambi\u00e9n la adici\u00f3n fotosensibilizada de metanol para la introducci\u00f3n directa de un fragmento hidroximetilo.     con estos intermedios sint\u00e9ticos se ha abordado la s\u00edntesis de la prostaglandina a2. Para introducir la cadena de la pga2 nos hemos basado en reac<\/p>\n<p>&nbsp;<\/p>\n<h3>Datos acad\u00e9micos de la tesis doctoral \u00ab<strong>Aplicaciones sint\u00e9ticas de los aductos de pauson-khand del norbomadieno. aproximaci\u00f3n a la s\u00edntesis de prostaglandinas y fitoprostanos<\/strong>\u00ab<\/h3>\n<ul>\n<li><strong>T\u00edtulo de la tesis:<\/strong>\u00a0 Aplicaciones sint\u00e9ticas de los aductos de pauson-khand del norbomadieno. aproximaci\u00f3n a la s\u00edntesis de prostaglandinas y fitoprostanos <\/li>\n<li><strong>Autor:<\/strong>\u00a0 Agust\u00ed Lled\u00f3 Ponsati <\/li>\n<li><strong>Universidad:<\/strong>\u00a0 Barcelona<\/li>\n<li><strong>Fecha de lectura de la tesis:<\/strong>\u00a0 08\/11\/2006<\/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>Antoni Riera Escale<\/li>\n<\/ul>\n<\/li>\n<li><strong>Tribunal<\/strong>\n<ul>\n<li>Presidente del tribunal: rafael Suau suarez <\/li>\n<li>roser Pleixats rovira (vocal)<\/li>\n<li>Miguel \u00e1ngel Peric\u00ed\u00a0s brondo (vocal)<\/li>\n<li>pelayo Camps Garc\u00eda (vocal)<\/li>\n<\/ul>\n<\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n","protected":false},"excerpt":{"rendered":"<p>Tesis doctoral de Agust\u00ed Lled\u00f3 Ponsati Se han optimizado metodolog\u00edas para la obtenci\u00f3n de aductos de pauson-khand del norbornadieno y [&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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