{"id":42712,"date":"1999-12-02T00:00:00","date_gmt":"1999-12-02T00:00:00","guid":{"rendered":"https:\/\/www.deberes.net\/tesis\/sin-categoria\/preparacion-en-forma-enantiopura-de-equivalentes-sinteticos-de-p-benzoquinona\/"},"modified":"1999-12-02T00:00:00","modified_gmt":"1999-12-02T00:00:00","slug":"preparacion-en-forma-enantiopura-de-equivalentes-sinteticos-de-p-benzoquinona","status":"publish","type":"post","link":"https:\/\/www.deberes.net\/tesis\/quimica\/preparacion-en-forma-enantiopura-de-equivalentes-sinteticos-de-p-benzoquinona\/","title":{"rendered":"Preparaci\u00f3n en forma enantiopura de equivalentes sint\u00e9ticos de p-benzoquinona"},"content":{"rendered":"<h2>Tesis doctoral de <strong> Jorge Medrano Rup\u00e9rez <\/strong><\/h2>\n<p>La presente tesis doctoral forma parte de un proyecto de investigaci\u00f3n que tiene como objetivo la preparaci\u00f3n de alcaloides de securinega. Para ello, se ha dise\u00f1ado una secuencia sint\u00e9tica en la cual uno de los pasos clave es una reacci\u00f3n de cicloadici\u00f3n, 1,3-dipolar entre una nitrona c\u00edclica y un monoacetal de p-benzoquinona. Para poder controlar la esteroselectividad del proceso de cicloadici\u00f3n y disminuir la cantidad de productos posibles, se han utilizado monoacetales enantiopuros de p-benzoquinona con simetr\u00eda c2, en los cuales se ha protegido previamente uno de los dos dobles enlaces mediante la adici\u00f3n conjugada de un tionucle\u00f3filo.  as\u00ed, se han sintetizado una serie de 1,2-dioles enantipuros con simetr\u00eda c2 de diferentes caracter\u00edsticas. A partir de ellos se han obtenido los correspondientes monoacetales enantiopuros con simetr\u00eda c2. Para ello se ha realizado previamente la optimizaci\u00f3n del proceso de acetalizaci\u00f3n.  se ha llevado a cabo un estudio de la reacci\u00f3n de adici\u00f3n conjugada de diferentes tionucle\u00f3filos utilizando la serie de monoacetales enantiopuros de p-benzoquinona obtenidos. Durante dicho estudio  se han podido aislar en forma enantiopura varios equivalentes sint\u00e9ticos de la p-benzoquinona con un grupo carbonilo protegido en forma de acetal y un doble enlace protegido mediante la adici\u00f3n conjugada de un tionucl\u00e9ofilo. De uno de ellos, (2r, 3r, 10s)-10-benzolito-2,3-diciclohexil-1,4-dioxaespiro (4.5)dec-6-en-8-ona, 94, se ha podido obtener una difracci\u00f3n de rayos x, determinando as\u00ed la configuraci\u00f3n absoluta de los tres centros estereog\u00e9nicos.  la cicloadici\u00f3n 1,3-dipolar de nitronas c\u00edclicas a olefinas de configuraci\u00f3n z son rgioselectivas y transcurren en la mayor\u00eda de los casos a trav\u00e9s de estados de transici\u00f3n de tipo exo de forma mayoritaria. Se ha realizado un estudio de la reacci\u00f3n de cicloadici\u00f3n 1,3-dipolar de las nitronas c\u00edclicas de 5 y 6 miembros a 94. En ambos casos se<\/p>\n<p>&nbsp;<\/p>\n<h3>Datos acad\u00e9micos de la tesis doctoral \u00ab<strong>Preparaci\u00f3n en forma enantiopura de equivalentes sint\u00e9ticos de p-benzoquinona<\/strong>\u00ab<\/h3>\n<ul>\n<li><strong>T\u00edtulo de la tesis:<\/strong>\u00a0 Preparaci\u00f3n en forma enantiopura de equivalentes sint\u00e9ticos de p-benzoquinona <\/li>\n<li><strong>Autor:<\/strong>\u00a0 Jorge Medrano Rup\u00e9rez <\/li>\n<li><strong>Universidad:<\/strong>\u00a0 Aut\u00f3noma de barcelona<\/li>\n<li><strong>Fecha de lectura de la tesis:<\/strong>\u00a0 12\/02\/1999<\/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>Pere De March Centelles<\/li>\n<\/ul>\n<\/li>\n<li><strong>Tribunal<\/strong>\n<ul>\n<li>Presidente del tribunal: josep Font cierco <\/li>\n<li>Jos\u00e9 Manuel Concell\u00f3n gracia (vocal)<\/li>\n<li>pedro Molina buend\u00eda (vocal)<\/li>\n<li>jordi Garc\u00eda g\u00f3mez (vocal)<\/li>\n<\/ul>\n<\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n","protected":false},"excerpt":{"rendered":"<p>Tesis doctoral de Jorge Medrano Rup\u00e9rez La presente tesis doctoral forma parte de un proyecto de investigaci\u00f3n que tiene como 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