{"id":87924,"date":"2018-03-10T00:12:46","date_gmt":"2018-03-10T00:12:46","guid":{"rendered":"https:\/\/www.deberes.net\/tesis\/sin-categoria\/sintesis-de-14-difosfinas-ciclopentanicas-enatiopuras-y-su-posible-uso-en-reducciones-enantioselectivas-cataliticas\/"},"modified":"2018-03-10T00:12:46","modified_gmt":"2018-03-10T00:12:46","slug":"sintesis-de-14-difosfinas-ciclopentanicas-enatiopuras-y-su-posible-uso-en-reducciones-enantioselectivas-cataliticas","status":"publish","type":"post","link":"https:\/\/www.deberes.net\/tesis\/quimica\/sintesis-de-14-difosfinas-ciclopentanicas-enatiopuras-y-su-posible-uso-en-reducciones-enantioselectivas-cataliticas\/","title":{"rendered":"Sintesis de 1,4-difosfinas ciclopentanicas enatiopuras y su posible uso en reducciones enantioselectivas cataliticas"},"content":{"rendered":"<h2>Tesis doctoral de <strong> Victoria Mu\u00f1oz-torrero Lopez-ibarra <\/strong><\/h2>\n<p>En la presente tesis doctoral se ha puesto a punto un m\u00e9todo general para la obtenci\u00f3n de (1a,2b,4b)-4(dialquilfosforil)-2-(difenilfosforilmetil) ciclopentanoles rac\u00e9micos por reacci\u00f3n de \u00f3xidos de trans-3,4-epoxiciclopentildialquilfosfinas epim\u00e9ricas con la sal de litio de la difenilmetilfosfina. Se ha procedido a la separaci\u00f3n de los enanti\u00f3meros de (1a,2b,4b)-2-(difenilfosforil)metil-4-(diisopropilfosforil)-ciclopentanol por reacci\u00f3n con isocianato de (s)-a-metilbencilo y posterior cristalizaci\u00f3n fraccionada de los carbamatos diastereom\u00e9ricos correspondientes.  por reducci\u00f3n de dichos carbamatos con hsicl3 se han podido obtener difosfinas 1,4-cis ciclopent\u00e1nicas que se han utilizado como ligando de rh(i) para la hidrogenaci\u00f3n catal\u00edtica enantioselectiva de a-(n-bencil-n-metil-amino)-3-hidroxi-acetofenona con el fin de obtener (r)-1-3-hidroxifenil)-2-(metilamino)etanol,(r)-fenilefrina, f\u00e1rmaco de la familia de las ariletanolaminas de gran interes industrial, si bien estos catalizadores no han mostrado una buena actividad catal\u00edtica ni enantioselectividad.  tambi\u00e9n se ha puesto a punto un procedimiento general estereoselectivo de obtenci\u00f3n de (1a,2b,3a)-3-(dialquilfosforil)-2-(difenilfosforilmetil) ciclopentanoles rac\u00e9micos por reacci\u00f3n de \u00f3xidos de 2,3-epoxiciclopentildialquilfosfinas epim\u00e9ricas con la sal del litio del \u00f3xido de la difenilmetilfosfina.  se ha puesto de manifiesto que el mecanismo de la reacci\u00f3n anterior implica la conversi\u00f3n de los \u00f3xidos de 2,3-epoxiciclopentildialquilfosfina epim\u00e9ricos en el mismo intermedio, la sal de litio de 3-(dialquilfosforil)-2-ciclopentenol, la cual experimenta una adici\u00f3n de michael por parte del carbani\u00f3n derivado del \u00f3xido de difenilmetilfosfina. Esta adici\u00f3n tiene lugar en forma estereoselectiva con adici\u00f3n del nucle\u00f3filo por la cara opuesta a aquella en la que se encuentra el grupo oli, seguido de protonaci\u00f3n del carbani\u00f3n a-por2 formado, probablemente e<\/p>\n<p>&nbsp;<\/p>\n<h3>Datos acad\u00e9micos de la tesis doctoral \u00ab<strong>Sintesis de 1,4-difosfinas ciclopentanicas enatiopuras y su posible uso en reducciones enantioselectivas cataliticas<\/strong>\u00ab<\/h3>\n<ul>\n<li><strong>T\u00edtulo de la tesis:<\/strong>\u00a0 Sintesis de 1,4-difosfinas ciclopentanicas enatiopuras y su posible uso en reducciones enantioselectivas cataliticas <\/li>\n<li><strong>Autor:<\/strong>\u00a0 Victoria Mu\u00f1oz-torrero Lopez-ibarra <\/li>\n<li><strong>Universidad:<\/strong>\u00a0 Barcelona<\/li>\n<li><strong>Fecha de lectura de la tesis:<\/strong>\u00a0 15\/12\/2000<\/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>Pelayo Camps Garc\u00eda<\/li>\n<\/ul>\n<\/li>\n<li><strong>Tribunal<\/strong>\n<ul>\n<li>Presidente del tribunal: jose Irurre perez <\/li>\n<li>angel Rodriguez de lera (vocal)<\/li>\n<li>Francisco Javier Sardina l\u00f3pez (vocal)<\/li>\n<li>josep Coll toledano (vocal)<\/li>\n<\/ul>\n<\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n","protected":false},"excerpt":{"rendered":"<p>Tesis doctoral de Victoria Mu\u00f1oz-torrero Lopez-ibarra En la presente tesis doctoral se ha puesto a punto un m\u00e9todo general para [&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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