{"id":61078,"date":"2018-03-09T22:48:55","date_gmt":"2018-03-09T22:48:55","guid":{"rendered":"https:\/\/www.deberes.net\/tesis\/sin-categoria\/new-catalytic-processes-based-on-cyclizations-of-allylstannanes-with-late-transition-metals\/"},"modified":"2018-03-09T22:48:55","modified_gmt":"2018-03-09T22:48:55","slug":"new-catalytic-processes-based-on-cyclizations-of-allylstannanes-with-late-transition-metals","status":"publish","type":"post","link":"https:\/\/www.deberes.net\/tesis\/quimica\/new-catalytic-processes-based-on-cyclizations-of-allylstannanes-with-late-transition-metals\/","title":{"rendered":"New catalytic processes based on cyclizations of allylstannanes with late transition metals"},"content":{"rendered":"<h2>Tesis doctoral de <strong> Susana Porcel Garc\u00eda <\/strong><\/h2>\n<p>Cap\u00edtulo 1.  nuestro grupo de investigaci\u00f3n hab\u00eda desarrollado un nuevo m\u00e9todo de obtenci\u00f3n de carbociclos de 5 o 6 miembros basado en el acoplamiento intramolecular de alilestannanos con alilacetatos catalizado por pd(0). A pesar de que los aspectos generales del mecanismo de la ciclaci\u00f3n se comprend\u00edan razonablemente bien, la estereoqu\u00edmica del proceso no era f\u00e1cil de justificar. As\u00ed,  mientras los carbociclos de 5 miembros se obten\u00edan con una configuraci\u00f3n relativa trans de los sustituyentes 1,2-dialquen\u00edlicos, los carbociclos de 6 miembros se obten\u00edan con una configuraci\u00f3n relativa cis. los carbociclos de 6 miembros con configuraci\u00f3n trans son de particular importancia, pues son precursores de lobanos como el fuscol y el lobatrieno, diterpenos de origen marino con potente actividad inhibidora de la bios\u00edntesis de leucotrienos.  Por esta raz\u00f3n como primer objetivo de este trabajo de tesis doctoral se propuso profundizar en el estudio de la esteroselectividad en la ciclaci\u00f3n de los sustratos precursores de los carbociclos de 6 miembros con el prop\u00f3sito de invertir la preferencia observada en la ciclaci\u00f3n.  se comenz\u00f3 analizando qu\u00e9 efecto ten\u00eda sobre la estereoselectividad de la reacci\u00f3n el empleo de fosfinas con caracter\u00edsticas est\u00e9ricas y\/o electr\u00f3nicas distintas. No obstante, en este estudio no se consigui\u00f3 mejorar los resultados obtenidos previamente.  paralelamente a la b\u00fasqueda de condiciones para la obtenci\u00f3n de carbociclos de 6 miembros con disposici\u00f3n trans-1,2-dialquenil de los sutituyentes, se encontr\u00f3 que los sustratos de tipo 1 dan la reacci\u00f3n de ciclaci\u00f3n con el complejo [rhcl(pph3)3], bajo condiciones similares a las empleadas en la cat\u00e1lisis con pd(0). Sorprendentemente, complejos de au(i) resultaron ser los catalizadores m\u00e1s activos para esta reacci\u00f3n de ciclaci\u00f3n. La reacci\u00f3n catalizada por au(i) es estrictamente dependiente de la configuraci\u00f3n del sustrato de partida y al igual que sucede con los comp<\/p>\n<p>&nbsp;<\/p>\n<h3>Datos acad\u00e9micos de la tesis doctoral \u00ab<strong>New catalytic processes based on cyclizations of allylstannanes with late transition metals<\/strong>\u00ab<\/h3>\n<ul>\n<li><strong>T\u00edtulo de la tesis:<\/strong>\u00a0 New catalytic processes based on cyclizations of allylstannanes with late transition metals <\/li>\n<li><strong>Autor:<\/strong>\u00a0 Susana Porcel Garc\u00eda <\/li>\n<li><strong>Universidad:<\/strong>\u00a0 Aut\u00f3noma de Madrid<\/li>\n<li><strong>Fecha de lectura de la tesis:<\/strong>\u00a0 26\/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>Antonio  M. Echavarren Pablos<\/li>\n<\/ul>\n<\/li>\n<li><strong>Tribunal<\/strong>\n<ul>\n<li>Presidente del tribunal: josep Bonjoch sese <\/li>\n<li>Juan  Carlos Carretero gonz\u00e1lvez (vocal)<\/li>\n<li>simeon Arseniyadis (vocal)<\/li>\n<li>Jos\u00e9 Luis Mascare\u00f1as cid (vocal)<\/li>\n<\/ul>\n<\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n","protected":false},"excerpt":{"rendered":"<p>Tesis doctoral de Susana Porcel Garc\u00eda Cap\u00edtulo 1. nuestro grupo de investigaci\u00f3n hab\u00eda desarrollado un nuevo m\u00e9todo de obtenci\u00f3n 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 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":[6775,17,416],"tags":[1384,51293,1417,29802,124883,134923],"class_list":["post-61078","post","type-post","status-publish","format-standard","hentry","category-organometalicos","category-quimica","category-quimica-organica","tag-antonio-m-echavarren-pablos","tag-jose-luis-mascarenas-cid","tag-josep-bonjoch-sese","tag-juan-carlos-carretero-gonzalvez","tag-simeon-arseniyadis","tag-susana-porcel-garcia"],"_links":{"self":[{"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/posts\/61078","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=61078"}],"version-history":[{"count":0,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/posts\/61078\/revisions"}],"wp:attachment":[{"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/media?parent=61078"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/categories?post=61078"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/tags?post=61078"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}