{"id":39357,"date":"1999-01-01T00:00:00","date_gmt":"1999-01-01T00:00:00","guid":{"rendered":"https:\/\/www.deberes.net\/tesis\/sin-categoria\/utilizacion-de-radicales-libres-en-quimica-organica-estudios-sobre-la-transposicion-de-brook-homolitica-estrategias-radicalarias-hacia-la-tetrodotoxina\/"},"modified":"1999-01-01T00:00:00","modified_gmt":"1999-01-01T00:00:00","slug":"utilizacion-de-radicales-libres-en-quimica-organica-estudios-sobre-la-transposicion-de-brook-homolitica-estrategias-radicalarias-hacia-la-tetrodotoxina","status":"publish","type":"post","link":"https:\/\/www.deberes.net\/tesis\/quimica\/utilizacion-de-radicales-libres-en-quimica-organica-estudios-sobre-la-transposicion-de-brook-homolitica-estrategias-radicalarias-hacia-la-tetrodotoxina\/","title":{"rendered":"Utilizacion de radicales libres en quimica organica: estudios sobre la  transposicion de brook homolitica. estrategias radicalarias hacia la  (-)-tetrodotoxina."},"content":{"rendered":"<h2>Tesis doctoral de <strong>  Paredes Boubeta M. Dolores <\/strong><\/h2>\n<p>Se estudi\u00f3 la posibilidad de generar radicales carbonados alfa-oxigenados utilizando como paso clave una transposici\u00f3n de brook homol\u00edtica. El tratamiento de alfa-hidroxisilanos con tetraacetato de plomo condujo a acetales mixtos, mientras que la fot\u00f3lisis de sus nitrito-derivados di\u00f3 lugar a los correspondientes compuestos carbon\u00edlicos, demostrando que la presencia de un \u00e1tomo de silicio en posici\u00f3n geminal a un grupo hidroxilo o a su nitrito modifica drasticamente la reactividad de estas funcionalidades. Se propone un modelo que en base a la sustituci\u00f3n explica la diferente evoluci\u00f3n observada hasta la fecha para radicales alcoxilo alfa-sililados.  se evalu\u00f3 la posible formaci\u00f3n de ciclopropanoles mediante una ciclaci\u00f3n radicalaria 1,3-exo-trig a acilsilanos. Se observ\u00f3 que la beta-fragmentaci\u00f3n del radical alcoxilo intermedio es m\u00e1s r\u00e1pida que la transposici\u00f3n de brook.  partiendo de la d-manosa y utilizando una adici\u00f3n radicalaria intramolecular 1,5-exo a \u00e9teres de cetoxima, se han preparado avanzados intermedios de la (-)-tetrodotoxina que poseen todos los \u00e1tomos de carbono de la mol\u00e9cula a excepci\u00f3n de c11 y la estereoqu\u00edmica correcta en las posiciones c7,c8,c8a y c9. Asimismo, en un sistema modelo y mediante una adici\u00f3n 1,3-dipolar intramolecular, ha sido posible preparar un intermedio que posee el anillo ciclohex\u00e1nico y el centro cuaternario nitrogenado presentes en la tetrodotoxina.<\/p>\n<p>&nbsp;<\/p>\n<h3>Datos acad\u00e9micos de la tesis doctoral \u00ab<strong>Utilizacion de radicales libres en quimica organica: estudios sobre la  transposicion de brook homolitica. estrategias radicalarias hacia la  (-)-tetrodotoxina.<\/strong>\u00ab<\/h3>\n<ul>\n<li><strong>T\u00edtulo de la tesis:<\/strong>\u00a0 Utilizacion de radicales libres en quimica organica: estudios sobre la  transposicion de brook homolitica. estrategias radicalarias hacia la  (-)-tetrodotoxina. <\/li>\n<li><strong>Autor:<\/strong>\u00a0  Paredes Boubeta M. Dolores <\/li>\n<li><strong>Universidad:<\/strong>\u00a0 Santiago de compostela<\/li>\n<li><strong>Fecha de lectura de la tesis:<\/strong>\u00a0 01\/01\/1999<\/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>Ricardo Alonso Alonso<\/li>\n<\/ul>\n<\/li>\n<li><strong>Tribunal<\/strong>\n<ul>\n<li>Presidente del tribunal: manuel G\u00f3mez guill\u00e9n <\/li>\n<li>Jos\u00e9 Luis Marco  contelles (vocal)<\/li>\n<li>enrique Guitian rivera (vocal)<\/li>\n<li>asuncion Barbero perez (vocal)<\/li>\n<\/ul>\n<\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n","protected":false},"excerpt":{"rendered":"<p>Tesis doctoral de Paredes Boubeta M. Dolores Se estudi\u00f3 la posibilidad de generar radicales carbonados alfa-oxigenados utilizando como paso clave [&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 center","background-size":"auto","background-attachment":"scroll","background-type":"","background-media":"","overlay-type":"","overlay-color":"","overlay-gradient":""},"tablet":{"background-color":"","background-image":"","background-repeat":"repeat","background-position":"center center","background-size":"auto","background-attachment":"scroll","background-type":"","background-media":"","overlay-type":"","overlay-color":"","overlay-gradient":""},"mobile":{"background-color":"","background-image":"","background-repeat":"repeat","background-position":"center center","background-size":"auto","background-attachment":"scroll","background-type":"","background-media":"","overlay-type":"","overlay-color":"","overlay-gradient":""}},"ast-content-background-meta":{"desktop":{"background-color":"var(--ast-global-color-5)","background-image":"","background-repeat":"repeat","background-position":"center center","background-size":"auto","background-attachment":"scroll","background-type":"","background-media":"","overlay-type":"","overlay-color":"","overlay-gradient":""},"tablet":{"background-color":"var(--ast-global-color-5)","background-image":"","background-repeat":"repeat","background-position":"center center","background-size":"auto","background-attachment":"scroll","background-type":"","background-media":"","overlay-type":"","overlay-color":"","overlay-gradient":""},"mobile":{"background-color":"var(--ast-global-color-5)","background-image":"","background-repeat":"repeat","background-position":"center center","background-size":"auto","background-attachment":"scroll","background-type":"","background-media":"","overlay-type":"","overlay-color":"","overlay-gradient":""}},"footnotes":""},"categories":[17,3209,49077,416,415,977],"tags":[101465,2802,2806,26,101464,35123],"class_list":["post-39357","post","type-post","status-publish","format-standard","hentry","category-quimica","category-quimica-de-los-hidratos-de-carbono","category-quimica-de-organosilicicos","category-quimica-organica","category-radicales-libres","category-santiago-de-compostela","tag-asuncion-barbero-perez","tag-enrique-guitian-rivera","tag-jose-luis-marco-contelles","tag-manuel-gomez-guillen","tag-paredes-boubeta-m-dolores","tag-ricardo-alonso-alonso"],"_links":{"self":[{"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/posts\/39357","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/comments?post=39357"}],"version-history":[{"count":0,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/posts\/39357\/revisions"}],"wp:attachment":[{"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/media?parent=39357"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/categories?post=39357"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/tags?post=39357"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}