{"id":80000,"date":"2018-03-09T23:25:54","date_gmt":"2018-03-09T23:25:54","guid":{"rendered":"https:\/\/www.deberes.net\/tesis\/sin-categoria\/nuevas-reacciones-de-ceteniminas-cicloadiciones-42-adiciones-radicalarias-y-reagrupamientos-sigmatropicos-15\/"},"modified":"2018-03-09T23:25:54","modified_gmt":"2018-03-09T23:25:54","slug":"nuevas-reacciones-de-ceteniminas-cicloadiciones-42-adiciones-radicalarias-y-reagrupamientos-sigmatropicos-15","status":"publish","type":"post","link":"https:\/\/www.deberes.net\/tesis\/quimica\/nuevas-reacciones-de-ceteniminas-cicloadiciones-42-adiciones-radicalarias-y-reagrupamientos-sigmatropicos-15\/","title":{"rendered":"Nuevas reacciones de ceteniminas: cicloadiciones [4+2], adiciones radicalarias y reagrupamientos sigmatr\u00f3picos [1,5]"},"content":{"rendered":"<h2>Tesis doctoral de <strong>  Ort\u00edn Avil\u00e9s Mar\u00eda Del Mar <\/strong><\/h2>\n<p>Se ha desarrollado una nueva metodolog\u00eda de s\u00edntesis de benzo[b]acridinas, basada en una reacci\u00f3n de cicloadici\u00f3n [4+2] intramolecular inducida t\u00e9rmicamente en c,c-difenil-n-[2-(2-propenil)fenil] ceteniminas, en la que una funci\u00f3n cetenimina act\u00faa como dieno totalmente carbonado y el doble enlace carbono-carbono del sustituyente 2-propenilo ejerce el papel de dien\u00f3filo.  as\u00ed mismo, se ha llevado a cabo el tratamiento t\u00e9rmico de n-[2-(2-propenil)-1-naftil]ceteniminas c,c-disustituidas y, dependiendo de los sustituyentes sobre el carbono terminal del fragmento cetenimina, se produce su ciclaci\u00f3n v\u00eda una reacci\u00f3n diels-alder intramolecular, para proporcionar  dibenzo[b,h]acridinas, y\/o v\u00eda migraci\u00f3n [1,5] de hidr\u00f3geno desde el \u00e1tomo de carbono sp3 del sustituyente 2-propenilo al \u00e1tomo de carbono central del fragmento cetenimina, seguido de un cierre electroc\u00edclico de anillo 6pi, para dar benzo[h]quinole\u00ednas.  se ha descrito, por primera vez, la participaci\u00f3n de ceteniminas en procesos radicalarios. Se ha llevado a cabo la adici\u00f3n intramolecular de radicales benc\u00edlicos generados desde grupos xantato y per\u00f3xidos org\u00e1nicos a dichos heterocumulenos obteni\u00e9ndose, v\u00eda radicales (indol-2-il)metilo intermedios, indoles sustituidos en la posici\u00f3n 2. La adici\u00f3n intramolecular a ceteniminas de radicales benc\u00edlicos cuando \u00e9stos se generan  desde bencil fenil seleniuros, por tratamiento con tris(trimetilsilil)silano en presencia de azoalcanos como aibn, conduce a 3-(1h-indol-2-il)propionitrilos, como resultado del acoplamiento cruzado selectivo de radicales (indol-2-il)metilo y del radical 1-ciano-1-metiletilo, proveniente del aibn. Estos \u00faltimos procesos de ciclaci\u00f3n radicalaria est\u00e1n controlados por el efecto del radical persistente.  tambi\u00e9n se ha investigado la adici\u00f3n de radicales ariloximetilo a ceteniminas, para lo que ha sido preciso desarrollar un nuevo m\u00e9todo de generaci\u00f3n de este tipo de radicales, que<\/p>\n<p>&nbsp;<\/p>\n<h3>Datos acad\u00e9micos de la tesis doctoral \u00ab<strong>Nuevas reacciones de ceteniminas: cicloadiciones [4+2], adiciones radicalarias y reagrupamientos sigmatr\u00f3picos [1,5]<\/strong>\u00ab<\/h3>\n<ul>\n<li><strong>T\u00edtulo de la tesis:<\/strong>\u00a0 Nuevas reacciones de ceteniminas: cicloadiciones [4+2], adiciones radicalarias y reagrupamientos sigmatr\u00f3picos [1,5] <\/li>\n<li><strong>Autor:<\/strong>\u00a0  Ort\u00edn Avil\u00e9s Mar\u00eda Del Mar <\/li>\n<li><strong>Universidad:<\/strong>\u00a0 Murcia<\/li>\n<li><strong>Fecha de lectura de la tesis:<\/strong>\u00a0 19\/05\/2006<\/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>Mateo Alajarin Ceron<\/li>\n<\/ul>\n<\/li>\n<li><strong>Tribunal<\/strong>\n<ul>\n<li>Presidente del tribunal: vicente Gotor santamar\u00eda <\/li>\n<li>albert Moyano baldoire (vocal)<\/li>\n<li>Jos\u00e9 Manuel Concell\u00f3n gracia (vocal)<\/li>\n<li>pedro Almendros requena (vocal)<\/li>\n<\/ul>\n<\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n","protected":false},"excerpt":{"rendered":"<p>Tesis doctoral de Ort\u00edn Avil\u00e9s Mar\u00eda Del Mar Se ha desarrollado una nueva metodolog\u00eda de s\u00edntesis de benzo[b]acridinas, basada 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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