{"id":53602,"date":"2018-03-09T22:41:16","date_gmt":"2018-03-09T22:41:16","guid":{"rendered":"https:\/\/www.deberes.net\/tesis\/sin-categoria\/a-computational-approach-to-the-synthesis-of-chiral-sulfoxides\/"},"modified":"2018-03-09T22:41:16","modified_gmt":"2018-03-09T22:41:16","slug":"a-computational-approach-to-the-synthesis-of-chiral-sulfoxides","status":"publish","type":"post","link":"https:\/\/www.deberes.net\/tesis\/quimica\/a-computational-approach-to-the-synthesis-of-chiral-sulfoxides\/","title":{"rendered":"A computational approach to the synthesis of chiral sulfoxides"},"content":{"rendered":"<h2>Tesis doctoral de <strong> David Balcells Badia <\/strong><\/h2>\n<p>La s\u00edntesis de sulf\u00f3xidos quirales ha sido investigada te\u00f3ricamente considerando dos de los m\u00e9todos m\u00e1s avanzados: la oxidaci\u00f3n asim\u00e9trica de sulfuros con per\u00f3xido de hidrogeno catalizada por vanadio y el m\u00e9todo dag.  el mecanismo de estas reacciones fue explorado a nivel dft (teor\u00eda del funcional de la densidad) en sistemas modelos. el origen de la enantioselectividad en los sistema reales fue investigado utilizando m\u00e9todos h\u00edbridos qm\/mm (mec\u00e1nica qu\u00e1ntica\/mec\u00e1nica molecular). El estudio dft sobre la sulfoxidaci\u00f3n asim\u00e9trica catalizada por vanadio revel\u00f3 que este proceso sigue un mecanismo de transferencia directa de ox\u00edgeno en el que el sustrato se oxida en una \u00fanica etapa concertada. El catalizador es un complejo de vanadio (+v) en que el oxidante se coordina al metal en modo hidroperoxo.  este complejo cataliza el proceso de oxidaci\u00f3n reduciendo la barrera energ\u00e9tica desde 40.4 a 26.7 kcal\/mol. El estudio qm\/mm en el sistema real demostr\u00f3 que existen dos diastere\u00f3meros del catalizador, etiquetados como a y b, que catolizan la oxidaci\u00f3n promoviendo enantisolectividades opuestas. La coexistencia de a y b en soluci\u00f3n permiti\u00f3 explicar la influencia de la estructura del ligando quieral sobre la enantioselectividad. El estudio dft del m\u00e9todo dag revel\u00f3 que la resoluci\u00f3n cin\u00e9tica din\u00e1mica implicada en esta reacci\u00f3n sigue un mecanismo de adici\u00f3n\/eliminaci\u00f3n. la etapa clave es la adici\u00f3n en al que el alcohol reacciona directamente con el cloruro de sulfinilo. este proceso implica una transferencia de hidrogeno que es asistida por una base. La trimetilamina reduce la barrera de este proceso desde 26.8 a 12.2 kcal\/mol. La base tambi\u00e9n cataliza la racemizaci\u00f3n del cloruro de sulfinilo reduciendo la barrera de su inversi\u00f3n piramidal desde 63.4 a 22.3 kcal\/mol. el desplazamiento inicial del cloruro por parte de la base fue descartado. El estudio qm\/mm del sistema real confirm\u00f3 que la enantioselectividad del proceso puede ser f\u00e1<\/p>\n<p>&nbsp;<\/p>\n<h3>Datos acad\u00e9micos de la tesis doctoral \u00ab<strong>A computational approach to the synthesis of chiral sulfoxides<\/strong>\u00ab<\/h3>\n<ul>\n<li><strong>T\u00edtulo de la tesis:<\/strong>\u00a0 A computational approach to the synthesis of chiral sulfoxides <\/li>\n<li><strong>Autor:<\/strong>\u00a0 David Balcells Badia <\/li>\n<li><strong>Universidad:<\/strong>\u00a0 Aut\u00f3noma de barcelona<\/li>\n<li><strong>Fecha de lectura de la tesis:<\/strong>\u00a0 29\/06\/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>Feliu Maseras Cuni<\/li>\n<\/ul>\n<\/li>\n<li><strong>Tribunal<\/strong>\n<ul>\n<li>Presidente del tribunal: gregorio Asensio aguilar <\/li>\n<li>josep Mar\u00eda Lluch l\u00f3pez (vocal)<\/li>\n<li>odile Eisenstein (vocal)<\/li>\n<li> Cossi\u00f3 mora Fernando pedro (vocal)<\/li>\n<\/ul>\n<\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n","protected":false},"excerpt":{"rendered":"<p>Tesis doctoral de David Balcells Badia La s\u00edntesis de sulf\u00f3xidos quirales ha sido investigada te\u00f3ricamente considerando dos de los m\u00e9todos [&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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