{"id":19582,"date":"2018-03-09T09:08:36","date_gmt":"2018-03-09T09:08:36","guid":{"rendered":"https:\/\/www.deberes.net\/tesis\/sin-categoria\/reacciones-aldolicas-estereoselectivas-de-enolatos-de-boro-aplicacion-a-la-sintesis-de-13-dioles\/"},"modified":"2018-03-09T09:08:36","modified_gmt":"2018-03-09T09:08:36","slug":"reacciones-aldolicas-estereoselectivas-de-enolatos-de-boro-aplicacion-a-la-sintesis-de-13-dioles","status":"publish","type":"post","link":"https:\/\/www.deberes.net\/tesis\/quimica\/reacciones-aldolicas-estereoselectivas-de-enolatos-de-boro-aplicacion-a-la-sintesis-de-13-dioles\/","title":{"rendered":"Reacciones aldolicas estereoselectivas de enolatos de boro. aplicaci\u00f3n a la sintesis de 1,3-dioles"},"content":{"rendered":"<h2>Tesis doctoral de <strong> Marta Galobardes Farr\u00e9s <\/strong><\/h2>\n<p>Las alfa-hidroxicetonas constituyen una familia de compuestos quirales que juegan un papel destacado en la formaci\u00f3n estereoselectiva de enlaces carbono-carbono. En este contexto, nuestro grupo de trabajo est\u00e1 interesado en profundizar en el estudio de la reactividad de los enolatos de titanio y boro de alfa-sililoxicetonas para desarrollar reacciones ald\u00f3licas altamente estereoselectivas que permitan completar con facilidad la s\u00edntesis de productos naturales.  en concreto en la presente tesis, se ha llevado a cabo la enolizaci\u00f3n de la (s)-2-tert-butildimetilsililoxi-3-pentanona y la (s)-2-tert-butildifenilsililoxi-3-pentanona con chx2bci.  se ha comprobado que el resultado de esta enolizaci\u00f3n es bastante dependiente de la naturaleza del grupo protector, la base i el disolvente. En efecto, se han optimizado estas variables en cada caso para poder obtener los aldoles sin o anti. Los aldoles sin-sin se han obtenido con excelentes rendimientos (76-92%) y diastereoselectividades (&gt;98:2) enolizando la cetona protegida con tert-butildimetilsililo con chx2bcl y et3n. Por el contrario, la enolizaci\u00f3n de la cetona protegida con tert-butildifenilsililo utilizando chx2bcl y etnme2 ha conducido a los aldoles sin-anti con excelentes rendimientos (78-87%) y diastereoselectividades moderadas (&gt;80:20).  as\u00ed mismo, se ha aprovechado la posibilidad que ofrecen los aldolatos de boro de ser tratados in situ con agentes reductores para obtener, en un solo paso, estructuras del tipo 2-metil-1,3-dioles sin-sin a partir de la (r)-2-tert-butildimetilsililoxi-3-pentanona con buenos rendimientos y control tasa de la estereoqu\u00edmica.  para demostrar la potencialidad sint\u00e9tica de las metodolog\u00edas desarrolladas se ha completado la s\u00edntesis del fragmento c1-c6 de las eritronlidas desde la (r)-2-tert-butildimetilsililoxi-3-pentanona en un total de 6 etapas con un rendimiento global del 12%, form\u00e1ndose tres de los cuatro estereocentros del fragmento<\/p>\n<p>&nbsp;<\/p>\n<h3>Datos acad\u00e9micos de la tesis doctoral \u00ab<strong>Reacciones aldolicas estereoselectivas de enolatos de boro. aplicaci\u00f3n a la sintesis de 1,3-dioles<\/strong>\u00ab<\/h3>\n<ul>\n<li><strong>T\u00edtulo de la tesis:<\/strong>\u00a0 Reacciones aldolicas estereoselectivas de enolatos de boro. aplicaci\u00f3n a la sintesis de 1,3-dioles <\/li>\n<li><strong>Autor:<\/strong>\u00a0 Marta Galobardes Farr\u00e9s <\/li>\n<li><strong>Universidad:<\/strong>\u00a0 Barcelona<\/li>\n<li><strong>Fecha de lectura de la tesis:<\/strong>\u00a0 23\/10\/2002<\/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>F\u00e9lix Urp\u00ed Tubella<\/li>\n<\/ul>\n<\/li>\n<li><strong>Tribunal<\/strong>\n<ul>\n<li>Presidente del tribunal: jaume Vilarrasa llorens <\/li>\n<li> Odriozola ibarguren Jos\u00e9 Manuel (vocal)<\/li>\n<li>odon Arjona loraque (vocal)<\/li>\n<li>jordi Bach ta\u00f1a (vocal)<\/li>\n<\/ul>\n<\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n","protected":false},"excerpt":{"rendered":"<p>Tesis doctoral de Marta Galobardes Farr\u00e9s Las alfa-hidroxicetonas constituyen una familia de compuestos quirales que juegan un papel destacado en [&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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