{"id":59848,"date":"2007-11-07T00:00:00","date_gmt":"2007-11-07T00:00:00","guid":{"rendered":"https:\/\/www.deberes.net\/tesis\/sin-categoria\/diseno-de-nuevos-sistemas-catala%c2%adticos-aplicaciones-en-alquilacion-ala%c2%adlica-asimetrica-y-formilacion-cianacion-nucleofa%c2%adlica-enantioselectiva\/"},"modified":"2007-11-07T00:00:00","modified_gmt":"2007-11-07T00:00:00","slug":"diseno-de-nuevos-sistemas-catala%c2%adticos-aplicaciones-en-alquilacion-ala%c2%adlica-asimetrica-y-formilacion-cianacion-nucleofa%c2%adlica-enantioselectiva","status":"publish","type":"post","link":"https:\/\/www.deberes.net\/tesis\/quimica-organica\/diseno-de-nuevos-sistemas-catala%c2%adticos-aplicaciones-en-alquilacion-ala%c2%adlica-asimetrica-y-formilacion-cianacion-nucleofa%c2%adlica-enantioselectiva\/","title":{"rendered":"Dise\u00f1o de nuevos sistemas catal\u00edticos: aplicaciones en alquilaci\u00f3n al\u00edlica asim\u00e9trica y formilaci\u00f3n\/cianaci\u00f3n nucleof\u00edlica enantioselectiva"},"content":{"rendered":"<h2>Tesis doctoral de <strong> David Monge Fern\u00e1ndez <\/strong><\/h2>\n<p>En esta tesis doctoral se han abordado distintos aspectos relacionados con la cat\u00e1lisis asim\u00e9trica. Por una parte la s\u00edntesis, el estudio estructural y de la actividad catal\u00edtica de nuevos complejos met\u00e1licos [pd(ii) y rh(i)] con ligandos mixtos c\/s quirales basados en carbenos n-heteroc\u00edclicos y tio\u00e9teres.Los complejos cati\u00f3nicos de pd(ii) han presentado actividad como catalizadores de la reacci\u00f3n de sustituci\u00f3n al\u00edlica, alcanzando enantioselectividades del 91%.Por otra parte, se han desarrollado sistemas catal\u00edticos para la formilaci\u00f3n\/cianaci\u00f3n enantioselectiva de equivalentes de enoato basados en el concepto de \u00abumpolung\u00bb. Los resultados obtenidos ampl\u00edan las perspectivas sint\u00e9ticas de la                                         1-metilenaminopirrolidina como sint\u00f3n d1, equivalente neutro de ani\u00f3n formilo y cianuro. La activaci\u00f3n catal\u00edtica de hidroxienonas mediante zn(otf)2\/t-bubox ha permitido la adici\u00f3n conjugada de                                              1-metilenaminopirrolidina con buen rendimiento y enantioselectividad (hasta 84% ee). Evidencias experimentales apoyan un modelo basado en una participaci\u00f3n clave del contrai\u00f3n triflato que ejercer\u00eda el control de la geometr\u00eda del complejo catalizador-sustrato mediante un puente de hidr\u00f3geno oh-otf. El potencial de la metodolog\u00eda se ilustra con la s\u00edntesis de ciano\u00e1cidos, precursores directos de \u00e1cidos amino but\u00edricos (gabas). la activaci\u00f3n organocatal\u00edtica de alquilid\u00e9n glioxilatos mediante tioureas quirales derivadas de aminoindanol (aminoalcohol comercialmente asequible en ambas formas enantiom\u00e9ricas) ha permitido la adici\u00f3n conjugada de 1-metilenaminopirrolidina con buen rendimiento y enantioselectividad (hasta 80% ee). Evidencias experimentales sugieren un modo de acci\u00f3n bifuncional del catalizador, mediante participaci\u00f3n de los nh \u00e1cidos y el grupo hidroxilo libre. La simplicidad operacional de este procedimiento y la alta versatilidad de los aductos confieren<\/p>\n<p>&nbsp;<\/p>\n<h3>Datos acad\u00e9micos de la tesis doctoral \u00ab<strong>Dise\u00f1o de nuevos sistemas catal\u00edticos: aplicaciones en alquilaci\u00f3n al\u00edlica asim\u00e9trica y formilaci\u00f3n\/cianaci\u00f3n nucleof\u00edlica enantioselectiva<\/strong>\u00ab<\/h3>\n<ul>\n<li><strong>T\u00edtulo de la tesis:<\/strong>\u00a0 Dise\u00f1o de nuevos sistemas catal\u00edticos: aplicaciones en alquilaci\u00f3n al\u00edlica asim\u00e9trica y formilaci\u00f3n\/cianaci\u00f3n nucleof\u00edlica enantioselectiva <\/li>\n<li><strong>Autor:<\/strong>\u00a0 David Monge Fern\u00e1ndez <\/li>\n<li><strong>Universidad:<\/strong>\u00a0 Sevilla<\/li>\n<li><strong>Fecha de lectura de la tesis:<\/strong>\u00a0 11\/07\/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>Rosario Fernandez Fernandez<\/li>\n<\/ul>\n<\/li>\n<li><strong>Tribunal<\/strong>\n<ul>\n<li>Presidente del tribunal:  Carretero gonz\u00e1lez j. Carlos <\/li>\n<li>ant\u00f3n Vidal i ferran (vocal)<\/li>\n<li>eduardo Peris fajarn\u00e9s (vocal)<\/li>\n<li>salvador Conejero iglesias (vocal)<\/li>\n<\/ul>\n<\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n","protected":false},"excerpt":{"rendered":"<p>Tesis doctoral de David Monge Fern\u00e1ndez En esta tesis doctoral se han abordado distintos aspectos relacionados con la cat\u00e1lisis asim\u00e9trica. [&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":[416,10715],"tags":[132187,132186,132185,48059,11339,46005],"class_list":["post-59848","post","type-post","status-publish","format-standard","hentry","category-quimica-organica","category-sevilla","tag-anton-vidal-i-ferran","tag-carretero-gonzalez-j-carlos","tag-david-monge-fernandez","tag-eduardo-peris-fajarnes","tag-rosario-fernandez-fernandez","tag-salvador-conejero-iglesias"],"_links":{"self":[{"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/posts\/59848","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=59848"}],"version-history":[{"count":0,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/posts\/59848\/revisions"}],"wp:attachment":[{"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/media?parent=59848"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/categories?post=59848"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/tags?post=59848"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}