{"id":67482,"date":"2018-03-09T22:55:55","date_gmt":"2018-03-09T22:55:55","guid":{"rendered":"https:\/\/www.deberes.net\/tesis\/sin-categoria\/oxifuncionalizacion-de-enlaces-csp3-h-con-metiltrifluorometildioxirano-mecanismo-y-selectividad\/"},"modified":"2018-03-09T22:55:55","modified_gmt":"2018-03-09T22:55:55","slug":"oxifuncionalizacion-de-enlaces-csp3-h-con-metiltrifluorometildioxirano-mecanismo-y-selectividad","status":"publish","type":"post","link":"https:\/\/www.deberes.net\/tesis\/mecanismos-de-las-reacciones-organicas\/oxifuncionalizacion-de-enlaces-csp3-h-con-metiltrifluorometildioxirano-mecanismo-y-selectividad\/","title":{"rendered":"Oxifuncionalizaci\u00f3n de enlaces c(sp3)-h con metil(trifluorometil)dioxirano: mecanismo y selectividad."},"content":{"rendered":"<h2>Tesis doctoral de <strong> Jaime Mart\u00ednez Ferrer <\/strong><\/h2>\n<p>1) las evidencias experimentales sobre la oxigenaci\u00f3n de enlaces c-h de adamantanos 2-sustitu\u00eddos con metil(trifluorometil)dioxirano descritas en este trabajo apoyan un mecanismo de inserci\u00f3n de ox\u00edgeno electrof\u00edlica y concertada para estas reacciones, con un estado de transici\u00f3n con deficiencia electr\u00f3nica significativa sobre el \u00e1tomo de carbono que reacciona. El mecanismo de la reacci\u00f3n no cambia al incrementar la desactivaci\u00f3n inductiva del sustrato.  2) la observaci\u00f3n de efectos cin\u00e9ticos isot\u00f3picos de deuterio a cuatro enlaces del centro reactivo en la oxigenaci\u00f3n de adamantanos 2-sustitu\u00eddos con metil(trifluorometil)dioxirano demuestran la trasmisi\u00f3n hiperconjugativa del efecto del sustituyente a trav\u00e9s de los enlaces # del sustrato. La ausencia de efectos del disolvente sobre la estereoselectividad de estas reacciones demuestra que \u00e9sta no est\u00e1 determinada por el efecto electrost\u00e1tico del sustituyente.   3) la velocidad y la regioselectividad encontradas en la oxigenaci\u00f3n de cadenas lineales de cuatro \u00e1tomos de carbono sustituidas muestran que el grupo trimetoxisililo es un sustituyente inductivo atrayente de electrones que, sin embargo, activa al \u00e1tomo de carbono en posici\u00f3n # frente a electr\u00f3filos. Este \u00faltimo efecto se atribuye a la deslocalizaci\u00f3n hiperconjugativa de los pares de electrones de los \u00e1tomos de ox\u00edgeno a trav\u00e9s de los enlaces si-c \u00f3 si-o.   4) 1,1,1-trifluoroacetona puede actuar como reactivo de abstracci\u00f3n de hidruro frente a alcoholes secundarios en presencia de dietiletoxialuminio. Este reactivo permite oxidar selectivamente alcoholes secundarios en presencia de alcoholes primarios.<\/p>\n<p>&nbsp;<\/p>\n<h3>Datos acad\u00e9micos de la tesis doctoral \u00ab<strong>Oxifuncionalizaci\u00f3n de enlaces c(sp3)-h con metil(trifluorometil)dioxirano: mecanismo y selectividad.<\/strong>\u00ab<\/h3>\n<ul>\n<li><strong>T\u00edtulo de la tesis:<\/strong>\u00a0 Oxifuncionalizaci\u00f3n de enlaces c(sp3)-h con metil(trifluorometil)dioxirano: mecanismo y selectividad. <\/li>\n<li><strong>Autor:<\/strong>\u00a0 Jaime Mart\u00ednez Ferrer <\/li>\n<li><strong>Universidad:<\/strong>\u00a0 Universitat de val\u00e9ncia (estudi general)<\/li>\n<li><strong>Fecha de lectura de la tesis:<\/strong>\u00a0 17\/10\/2008<\/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>Mar\u00eda Elena Gonz\u00e1lez Nu\u00f1ez<\/li>\n<\/ul>\n<\/li>\n<li><strong>Tribunal<\/strong>\n<ul>\n<li>Presidente del tribunal: Miguel \u00e1ngel Miranda alonso <\/li>\n<li>pedro Jos\u00e9 Campos Garc\u00eda (vocal)<\/li>\n<li>pedro Miguel Carda us\u00f3 (vocal)<\/li>\n<li>pedro Antonio Aleman lopez (vocal)<\/li>\n<\/ul>\n<\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n","protected":false},"excerpt":{"rendered":"<p>Tesis doctoral de Jaime Mart\u00ednez Ferrer 1) las evidencias experimentales sobre la oxigenaci\u00f3n de enlaces c-h de adamantanos 2-sustitu\u00eddos con [&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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