{"id":61021,"date":"2018-03-09T22:48:51","date_gmt":"2018-03-09T22:48:51","guid":{"rendered":"https:\/\/www.deberes.net\/tesis\/sin-categoria\/sa%c2%adntesis-de-4-y-5-alqueniltiazoles-y-su-reactividad-frente-a-dienofilos\/"},"modified":"2018-03-09T22:48:51","modified_gmt":"2018-03-09T22:48:51","slug":"sa%c2%adntesis-de-4-y-5-alqueniltiazoles-y-su-reactividad-frente-a-dienofilos","status":"publish","type":"post","link":"https:\/\/www.deberes.net\/tesis\/quimica\/sa%c2%adntesis-de-4-y-5-alqueniltiazoles-y-su-reactividad-frente-a-dienofilos\/","title":{"rendered":"S\u00edntesis de 4- y 5-alqueniltiazoles y su reactividad frente a dien\u00f3filos"},"content":{"rendered":"<h2>Tesis doctoral de <strong> Jos\u00e9 Cabrera Crespo <\/strong><\/h2>\n<p>En esta memoria se ha demostrado que los 4-alqueniltiazoles sintetizados participan en reacciones de diels-alder de demanda electr\u00f3nica normal, actuando como fragmento di\u00e9nico el que forman el doble enlace c-c formal del anillo de tiazol y el doble enlace alquen\u00edlico. Los 2-fenil y 2-metil-4-alqueniltiazoles s\u00f3lo reaccionan con los carbodien\u00f3filos m\u00e1s reactivos, evolucionando el correspondiente aducto de la cicloadici\u00f3n en el medio de reacci\u00f3n mediante una migraci\u00f3n 1,3 de hidr\u00f3geno, aunque en algunos casos el aducto primario experimenta deshidrogenaci\u00f3n o reacciona con una segunda mol\u00e9cula de dien\u00f3filo, generalmente, mediante una reacci\u00f3n \u00abene\u00bb. Las reacciones de estos sustratos con el heterodien\u00f3filo 4-fenil-1,2,4-triazolin-3,5-diona (ptad) rinden los correspondientes cicloaductos primarios. Todos estos procesos son altamente estereocontrolados, proporcionando de forma mayoritaria el cicloaducto resultante de una aproximaci\u00f3n endo del dien\u00f3filo. Se ha propuesto que los 2-fenil y 2-metil-4-alqueniltiazoles reaccionan con los carbodien\u00f3filos ensayados mediante un mecanismo concertado aunque, posiblemente, a trav\u00e9s de un estado de transici\u00f3n altamente polarizado. Por el contrario, el estudio computacional del mecanismo de las reacciones de estos sustratos con htad al nivel de teor\u00eda b3lyp\/6-31+g** muestra que dichas reacciones pueden transcurrir bien mediante un mecanismo concertado con un estado de transici\u00f3n altamente asincr\u00f3nico o bien mediante un mecanismo en etapas a trav\u00e9s de un intermedio dipolar de vida extremadamente corta. del estudio de la diastereoselectividad facial de este tipo de procesos, empleando tiazoles con un centro estereog\u00e9nico en el carbono \u00edY del doble enlace c-c alquen\u00edlico, se deduce que el grado de diastereoselecci\u00f3n es moderado. Seg\u00fan el modelo propuesto para explicar el curso estereoqu\u00edmico del proceso, \u00e9ste se encuentra controlado por factores est\u00e9ricos. la degradaci\u00f3n del anillo de tiazol mediante trat<\/p>\n<p>&nbsp;<\/p>\n<h3>Datos acad\u00e9micos de la tesis doctoral \u00ab<strong>S\u00edntesis de 4- y 5-alqueniltiazoles y su reactividad frente a dien\u00f3filos<\/strong>\u00ab<\/h3>\n<ul>\n<li><strong>T\u00edtulo de la tesis:<\/strong>\u00a0 S\u00edntesis de 4- y 5-alqueniltiazoles y su reactividad frente a dien\u00f3filos <\/li>\n<li><strong>Autor:<\/strong>\u00a0 Jos\u00e9 Cabrera Crespo <\/li>\n<li><strong>Universidad:<\/strong>\u00a0 Murcia<\/li>\n<li><strong>Fecha de lectura de la tesis:<\/strong>\u00a0 25\/10\/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>Mateo Alajarin Ceron<\/li>\n<\/ul>\n<\/li>\n<li><strong>Tribunal<\/strong>\n<ul>\n<li>Presidente del tribunal: Miguel \u00e1ngel Yus astiz <\/li>\n<li>Fernando Lopez ortiz (vocal)<\/li>\n<li>carmen N\u00e1jera domingo (vocal)<\/li>\n<li>isabel Mar\u00eda Saura llamas (vocal)<\/li>\n<\/ul>\n<\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n","protected":false},"excerpt":{"rendered":"<p>Tesis doctoral de Jos\u00e9 Cabrera Crespo En esta memoria se ha demostrado que los 4-alqueniltiazoles sintetizados participan en reacciones de [&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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