{"id":61711,"date":"2007-03-12T00:00:00","date_gmt":"2007-03-12T00:00:00","guid":{"rendered":"https:\/\/www.deberes.net\/tesis\/sin-categoria\/sintesis-total-del-core-de-rac-tetrodotoxina\/"},"modified":"2007-03-12T00:00:00","modified_gmt":"2007-03-12T00:00:00","slug":"sintesis-total-del-core-de-rac-tetrodotoxina","status":"publish","type":"post","link":"https:\/\/www.deberes.net\/tesis\/estereoquimica-y-analisis-conformacional\/sintesis-total-del-core-de-rac-tetrodotoxina\/","title":{"rendered":"Sintesis total del core de rac-tetrodotoxina"},"content":{"rendered":"<h2>Tesis doctoral de <strong> Sergio Maroto Quintana <\/strong><\/h2>\n<p>La tetrodotoxina (ttx) es un alcaloide guanid\u00ednio de elevada complejidad estructural cuya fuente natural m\u00e1s com\u00fan son ciertas especies de pez globo (orden tetraodontidae). Es una potente neurotoxina que bloquea selectivamente los canales de sodio dependientes del voltaje, inhibiendo el transporte de iones sodio a trav\u00e9s de la membrana de neuronas y otras c\u00e9lulas excitables.  en esta tesis doctoral se desarrolla una estrategia sint\u00e9tica, intr\u00ednsicamente enantiodivergente, que permitir\u00e1 obtener ambos enanti\u00f3meros de la ttx y su rac\u00e9mico empleando la simetr\u00eda como herramienta estrat\u00e9gica.    se ha conseguido la s\u00edntesis total de dos equivalentes sint\u00e9ticos del core de rac-ttx, estructuras e, con un rendimiento global del 9,5%, en 13 etapas, a partir de sustratos de partida comerciales. Estas estructuras incorporan el esqueleto ciclohex\u00e1nico hexasustituido de ttx (con diez de los once carbonos del producto natural) que contiene, con la estereoqu\u00edmica relativa apropiada, el puente carbonado del orto\u00e9ster (c9 y c10) y el nitr\u00f3geno n1 que soporta el grupo guanidinio enmascarados como una  -lactama, los carbonos convenientemente sustituidos c4 y c11, y las posiciones oxigenadas c5, c6, c7 y c8. Presentan seis centros estereog\u00e9nicos, dos de ellos cuaternarios en disposici\u00f3n 1,4 (c6 y c8a), y la funcionalidad adecuada para introducir el hidroxilo de c9 y los grupos orto\u00e9ster, hemiaminal y guanidina caracter\u00edsticos de ttx.    las etapas clave a destacar del esquema sint\u00e9tico desarrollado para la preparaci\u00f3n de la cianhidrina e (core de rac-ttx) son las siguientes:  1. Reacci\u00f3n de ciclaci\u00f3n intramolecular con desaromatizaci\u00f3n oxidativa de las n alcoxiamida  derivadas del cloruro de p-metoxifenilacetilo (comercial) para dar lugar al ciclohexadieno-espiro-?-Lactamas a meso (aquiral) y enantiom\u00e9ricamente pura (quiral). 2. Dihidroxilaci\u00f3n diastereoselectiva de las dienonas a meso o quiral por su cara   (anti al n1) generando los dioles b rac\u00e9mic<\/p>\n<p>&nbsp;<\/p>\n<h3>Datos acad\u00e9micos de la tesis doctoral \u00ab<strong>Sintesis total del core de rac-tetrodotoxina<\/strong>\u00ab<\/h3>\n<ul>\n<li><strong>T\u00edtulo de la tesis:<\/strong>\u00a0 Sintesis total del core de rac-tetrodotoxina <\/li>\n<li><strong>Autor:<\/strong>\u00a0 Sergio Maroto Quintana <\/li>\n<li><strong>Universidad:<\/strong>\u00a0 Aut\u00f3noma de Madrid<\/li>\n<li><strong>Fecha de lectura de la tesis:<\/strong>\u00a0 03\/12\/2007<\/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>Pedro Noheda Marin<\/li>\n<\/ul>\n<\/li>\n<li><strong>Tribunal<\/strong>\n<ul>\n<li>Presidente del tribunal: Jos\u00e9 Luis Garc\u00eda ruano <\/li>\n<li>gregorio Asensio aguilar (vocal)<\/li>\n<li>julio Delgado mart\u00edn (vocal)<\/li>\n<li>antoni Torrens jover (vocal)<\/li>\n<\/ul>\n<\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n","protected":false},"excerpt":{"rendered":"<p>Tesis doctoral de Sergio Maroto Quintana La tetrodotoxina (ttx) es un alcaloide guanid\u00ednio de elevada complejidad estructural cuya fuente natural [&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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