{"id":38452,"date":"2018-03-09T09:38:01","date_gmt":"2018-03-09T09:38:01","guid":{"rendered":"https:\/\/www.deberes.net\/tesis\/sin-categoria\/aproximacion-sintetica-a-la-macrolactina-a\/"},"modified":"2018-03-09T09:38:01","modified_gmt":"2018-03-09T09:38:01","slug":"aproximacion-sintetica-a-la-macrolactina-a","status":"publish","type":"post","link":"https:\/\/www.deberes.net\/tesis\/quimica\/aproximacion-sintetica-a-la-macrolactina-a\/","title":{"rendered":"Aproximacion sintetica a la macrolactina a."},"content":{"rendered":"<h2>Tesis doctoral de <strong> Angel Gonzalez Solana <\/strong><\/h2>\n<p>Se han preparado los fragmentos c5-c12 y c13-c24 de la macrolactina a con buen rendimiento qu\u00edmico y estereoselectividad. Las etapas claves han sido las reacciones ald\u00f3licas del acetato entre aldeh\u00eddos alfa, beta y gamma-insaturados y unos sintones an\u00e1logos de acetato.  los aldeh\u00eddos empleados eran los fragmentos c7-c12 y c15-c24 de la macrolactona. El primero de ellos se prepar\u00f3, mediante una reacci\u00f3n de heck, con un rendimiento global del 90%, estereoselectividad de 98 a 2 y a escala multigramo. El segundo, el aldeh\u00eddo m\u00e1s elaborado, se sintetiz\u00f3 con un 50% de rendimiento global, 95 a 5 de estereoselectividad en 9 etapas a partir del (s)-lactato de etilo; para alargar la cadena carbonada se hizo uso de reacciones de wittig y de horner-wadsworth-emmons.  en lo que respecta a las reacciones ald\u00f3licas del acetato se desarroll\u00f3 una metodolog\u00eda con buen rendimiento qu\u00edmico (90%) y diastereoselectividad (90%) utilizando el auxiliar quiral desarrollado por nagao pero con tetracloruro de titanio como \u00e1cido de lewis y n- etildiisopropilamina como base. Tambi\u00e9n se ha comprobado que dicho procedimiento resulta ser m\u00e1s eficiente y asequible que otros existentes en la literatura, como es:  el \u00e1cido de lewis quiral desarrollado por gennari, una reacci\u00f3n ald\u00f3lica tipo mukaiyama con el catalizador quiral de keck y con el auxiliar quiral de nagao seg\u00fan su mismo protocolo, esto es, con triflato de esta\u00f1o (ii) y n etilpiperidina.  por \u00faltimo, se protegieron los hidroxilos as\u00ed obtenidos y se estudiaron las modificaciones de los grupos funcionales en el c12 y c13 para formar el enlace entre ambos carbonos. En este sentido se optimizaron unas secuencias sint\u00e9ticas para funcionalizar el c13 como ditiano y el c12 como hal\u00edlico.<\/p>\n<p>&nbsp;<\/p>\n<h3>Datos acad\u00e9micos de la tesis doctoral \u00ab<strong>Aproximacion sintetica a la macrolactina a.<\/strong>\u00ab<\/h3>\n<ul>\n<li><strong>T\u00edtulo de la tesis:<\/strong>\u00a0 Aproximacion sintetica a la macrolactina a. <\/li>\n<li><strong>Autor:<\/strong>\u00a0 Angel Gonzalez Solana <\/li>\n<li><strong>Universidad:<\/strong>\u00a0 Barcelona<\/li>\n<li><strong>Fecha de lectura de la tesis:<\/strong>\u00a0 15\/07\/1998<\/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>Jaume Vilarrasa Llorens<\/li>\n<\/ul>\n<\/li>\n<li><strong>Tribunal<\/strong>\n<ul>\n<li>Presidente del tribunal: serafin Valverde l\u00f3pez <\/li>\n<li>Jos\u00e9 Mar\u00eda Lassaletta simon (vocal)<\/li>\n<li>jordi Marquet cortes (vocal)<\/li>\n<li>josep Bonjoch sese (vocal)<\/li>\n<\/ul>\n<\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n","protected":false},"excerpt":{"rendered":"<p>Tesis doctoral de Angel Gonzalez Solana Se han preparado los fragmentos c5-c12 y c13-c24 de la macrolactina a con buen [&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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