{"id":105990,"date":"2018-03-11T10:29:43","date_gmt":"2018-03-11T10:29:43","guid":{"rendered":"https:\/\/www.deberes.net\/tesis\/sin-categoria\/nuevas-metodologa%c2%adas-para-la-sa%c2%adntesis-asimetrica-de-centros-benca%c2%adlicos-cuaternarios\/"},"modified":"2018-03-11T10:29:43","modified_gmt":"2018-03-11T10:29:43","slug":"nuevas-metodologa%c2%adas-para-la-sa%c2%adntesis-asimetrica-de-centros-benca%c2%adlicos-cuaternarios","status":"publish","type":"post","link":"https:\/\/www.deberes.net\/tesis\/quimica-organica\/nuevas-metodologa%c2%adas-para-la-sa%c2%adntesis-asimetrica-de-centros-benca%c2%adlicos-cuaternarios\/","title":{"rendered":"Nuevas metodolog\u00edas para la s\u00edntesis asim\u00e9trica de centros benc\u00edlicos cuaternarios."},"content":{"rendered":"<h2>Tesis doctoral de <strong> Esther Torrente De Haro <\/strong><\/h2>\n<p>La tesis doctoral de d\u00aa esther torrente de haro ha permitido desarrollar una metodolog\u00eda eficaz basada en el empleo de bencilcarbaniones sulfinilados como nucle\u00f3filos, en que el grupo sulfinilo no se encuentra unido a la posici\u00f3n orto de un anillo arom\u00e1tico vecino, actuando como auxiliar quiral remoto.  los resultados de los distintos procesos estudiados, se pueden cifrar en los siguientes puntos: 1.\tSe han descrito condiciones experimentales en las que el grupo sulfinilo es capaz de controlar la formaci\u00f3n estereoselectiva de carbonos cuaternarios benc\u00edlicos mediante reacci\u00f3n de los aniones benc\u00edlicos derivados de \u00c2\u00bf-alquilfenilacetonitrilos con electr\u00f3filos t\u00edpicos de procesos de alquilaci\u00f3n. Las especies ani\u00f3nicas intermedias han podido identificarse mediante estudios de resonancia magn\u00e9tica nuclear. 2.\tEsta metodolog\u00eda se ha aplicado a la s\u00edntesis de 1,6-eninos enantiom\u00e9ricamente puros con el fin de estudiar su comportamiento en condiciones de cicloadici\u00f3n de pauson-khand. Se ha constatado el papel fundamental desempe\u00f1ado por el grupo sulfinilo como auxiliar quiral remoto, cuya presencia ha permitido optimizar la obtenci\u00f3n de derivados benc\u00edlicos de ciclopentenona portadores de tres estereocentros. 3. \tSe ha desarrollado la s\u00edntesis asim\u00e9trica de \u00c2\u00bf-alquil \u00c2\u00bf-aril \u00c2\u00bf-cianoacetatos y \u00c2\u00bf-alquil \u00c2\u00bf-aril \u00c2\u00bf-acilacetonitrilos enantiom\u00e9ricamente enriquecidos, derivados de \u00e1cidos mal\u00f3nicos mediante procesos de carbonilaci\u00f3n y alcoxicarbonilaci\u00f3n asim\u00e9trica de los sulfinil carbaniones benc\u00edlicos descritos. 4.\tSe ha podido constatar la gran eficacia de la funci\u00f3n del azufre quiral presente en los sulfinilbencilcarbaniones estudiados como inductor quiral de la estereoselectividad de las reacciones de adici\u00f3n conjugada en presencia de compuestos carbon\u00edlicos \u00c2\u00bf,\u00c2\u00bf-insaturados tanto c\u00edclicos como ac\u00edclicos, como aceptores de michael. los resultados alcanzados durante el desarrollo de la tesis doctoral han dado lugar a las siguientes publicaciones en revistas cient\u00edficas internacionales:   \u00c2\u00bfstereodivergent quaternization of 2-alkyl-2-p-tolylsulfinylacetonitriles. Nmr spectroscopic evidence of planar and pyramidal benzylic carbanions\u00c2\u00bf l. Garc\u00eda ruano, a. M. Mart\u00edn castro, f. Tato, e. Torrente, a. M. Poveda, chemistry \u00c2\u00bf a european journal 16, 6317-6325 (2010). \u00c2\u00bfdiastereodivergent synthesis of benzylic quaternary centers mediated by a remote sulfinyl group. Spectroscopic evidences of the structure of the carbanionic intermediates\u00c2\u00bf j. L. Garc\u00eda ruano, a. M. Mart\u00edn castro, e. Torrente, a. M. Poveda, phosphorous, sulfur and silicon and the related elements 186:5, 1119-1129 (2011).  \u00c2\u00bfasymmetric synthesis of benzylic quaternary difunctionalized carbons mediated by a remote sulfinyl group\u00c2\u00bf j. L. Garc\u00eda ruano, e. Torrente, a. M. Mart\u00edn castro journal of organic chemistry 76, 3597\u00c2\u00bf3603 (2011).  \u00c2\u00bfasymmetric intramolecular pauson\u00c2\u00bfkhand reaction mediated by a remote sulfenyl or sulfinyl group\u00c2\u00bf j. L. Garc\u00eda ruano, e. Torrente, a. Parra, j. Alem\u00e1n, a. M. Mart\u00edn castro, journal of organic chemistry 77, 6583-6599 (2012). \u00c2\u00bfuse of lithiated chiral o\u00c2\u00bfsulfinylbenzyl carbanions for the one-pot building of linear fragments containing up to four connected stereocenters\u00c2\u00bf j. L. Garc\u00eda ruano, e. Torrente, a. M. Mart\u00edn castro journal of organic chemistry 78, 647-657 (2013). \tasimismo, durante el desarrollo de la tesis doctoral, d\u00aa esther torrente ha realizado dos estancias predoctorales en el marco de sendas colaboraciones con los grupos de investigaci\u00f3n del profesor saverio florio (universit\u00ed\u00a0 degli studio di bari, italia), y el profesor alessandro degl`innocenti (universit\u00ed\u00a0 degli studio di firenze, italia). Los trabajos realizados durante dichas estancias han dado lugar a las siguientes publicaciones:   \u00c2\u00bfinfluence of an ortho-sulfinyl group on the configurational stability of \u00c2\u00bf-lithiated aryloxiranes: deuteration of tolylsulfinyl styrene oxides\u00c2\u00bf v. Capriati , s. Florio, r. Luisi, a. Salomone, m. G. Tocco, a. M. Mart\u00edn castro, j. L. Garc\u00eda ruano, e. Torrente, tetrahedron 65, 383-388 (2009).   \u00c2\u00bfstereoselective synthesis of 2,3-epoxy alcohols mediated by a remote sulfinyl group\u00c2\u00bf j. L. Garc\u00eda ruano, a. M. Mart\u00edn castro, f. Tato, e. Torrente, m. G. Tocco, s. Florio, v. Capriati tetrahedron 66, 1581-1585 (2010). \t                \u00c2\u00bfsynthesis of enantiomerically pure 1,2-disubstituted 2-selenoamines\u00c2\u00bf a. Degl\u00c2\u00bfinnocenti, a. Capperucci, l. Frateschi, j. L. Garc\u00eda ruano, a. M. Mart\u00edn castro, e. Torrente  phosphorous, sulfur and silicon and the related elements 186:5, 1268-1273 (2011).                    \u00c2\u00bfsynthesis of enantiomerically pure anti-1,2-diaryl and syn-1,2-alkylaryl vic-selenoamines\u00c2\u00bf j. L. Garc\u00eda ruano, e. Torrente, i. Alonso, m. Rodriguez, a. M. Mart\u00edn castro, a. Degl\u00c2\u00bfinnocenti, l. Frateschi, a. Capperucci journal of organic chemistry 77, 1974-1982 (2012).<\/p>\n<p>&nbsp;<\/p>\n<h3>Datos acad\u00e9micos de la tesis doctoral \u00ab<strong>Nuevas metodolog\u00edas para la s\u00edntesis asim\u00e9trica de centros benc\u00edlicos cuaternarios.<\/strong>\u00ab<\/h3>\n<ul>\n<li><strong>T\u00edtulo de la tesis:<\/strong>\u00a0 Nuevas metodolog\u00edas para la s\u00edntesis asim\u00e9trica de centros benc\u00edlicos cuaternarios. <\/li>\n<li><strong>Autor:<\/strong>\u00a0 Esther Torrente De Haro <\/li>\n<li><strong>Universidad:<\/strong>\u00a0 Aut\u00f3noma de Madrid<\/li>\n<li><strong>Fecha de lectura de la tesis:<\/strong>\u00a0 17\/12\/2010<\/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>Jos\u00e9 Luis Garc\u00eda Ruano<\/li>\n<\/ul>\n<\/li>\n<li><strong>Tribunal<\/strong>\n<ul>\n<li>Presidente del tribunal: Miguel \u00e1ngel Peric\u00ed\u00a0s brondo <\/li>\n<li>inmaculada Fernandez fernandez (vocal)<\/li>\n<li>benito Alcaide ala\u00f1on (vocal)<\/li>\n<li>ines Alonso montero (vocal)<\/li>\n<\/ul>\n<\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n","protected":false},"excerpt":{"rendered":"<p>Tesis doctoral de Esther Torrente De Haro La tesis doctoral de d\u00aa esther torrente de haro ha permitido desarrollar una 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