{"id":113225,"date":"2018-03-11T10:40:35","date_gmt":"2018-03-11T10:40:35","guid":{"rendered":"https:\/\/www.deberes.net\/tesis\/sin-categoria\/hydrazides-and-hydrazones-as-versatile-michael-donors-for-iminium-catalyzed-conjugate-addition-reactions\/"},"modified":"2018-03-11T10:40:35","modified_gmt":"2018-03-11T10:40:35","slug":"hydrazides-and-hydrazones-as-versatile-michael-donors-for-iminium-catalyzed-conjugate-addition-reactions","status":"publish","type":"post","link":"https:\/\/www.deberes.net\/tesis\/mecanismos-de-las-reacciones-organicas\/hydrazides-and-hydrazones-as-versatile-michael-donors-for-iminium-catalyzed-conjugate-addition-reactions\/","title":{"rendered":"Hydrazides and hydrazones as versatile michael-donors for iminium-catalyzed conjugate addition reactions"},"content":{"rendered":"<h2>Tesis doctoral de <strong> Maitane Fernandez Chento <\/strong><\/h2>\n<p>Abstractin the work compiled in this thesis is presented a series of strategies that have been studied and have lead to the asymmetric synthesis of useful building blocks in high yields and stereochemical control. These are reliant on the use of chiral secondary amines as the element that induces stereocontrol, where the activation of the substrate is based on the formation of an iminium ion intermediate within the catalytic cycle. In this sense, it has been demonstrated that, under this type of activation, hydrazides and hydrazones are efficient and versatile reagents that can be used as michael donors in conjugate addition reactions.Thus, the performance of these hydrazide and hydrazone reagents as n-donors has been initially tested. In this context, two different aza-michael initiated cascade reactions have been studied, using either n,n\u00c2\u00bf-disubstituted hydrazides or hydrazones derived from pyruvaldehyde in the reaction with -unsaturated aldehydes. Furthermore, the synthetic versatility of the products obtained has allowed a series of transformations to be performed, which is highlighted in the synthesis of valuable adducts (e.G. Pyrazolines, pyrazolidinones or 1,3-diamines).On the other hand, the ability of hydrazones to act c-pro-nucleophiles for the same type of reaction has also been demonstrated. In this sense, the conjugate addition reaction between n-monosubstituted hydrazones and various enals via iminium activation has been studied, confirming that hydrazones containing an electron-withdrawing group at the azomethine position undergo this process in a highly efficient manner. Moreover, the importance of this methodology has been highlighted by the synthesis of a series of 1,4-dicarbonyl compounds, verifying that hydrazones can behave as acyl anion equivalents.Resumenen el trabajo de investigaci\u00f3n recogido en la presente memoria se han estudiado una serie de estrategias que tienen como finalidad la s\u00edntesis asim\u00e9trica de compuestos de inter\u00e9s con elevado rendimiento y control estereoqu\u00edmico. \u00e9stas est\u00e1n enmarcadas en el uso de aminas secundarias quirales a modo de elementos estereocontroladores, donde el tipo de activaci\u00f3n del sustrato de partida se basa en la formaci\u00f3n de iones iminio. En este sentido, se ha demostrado que las hidrazidas e hidrazonas son dadores de michael vers\u00e1tiles y eficientes, que pueden ser aplicados a reacciones de adici\u00f3n conjugada bajo este tipo de activaci\u00f3n.As\u00ed, en un primer lugar se ha evaluado la aplicabilidad de estas hidrazidas e hidrazonas como nucle\u00f3filos nitrogenados. En este contexto, se han estudiado dos reacciones en cascada iniciadas por reacciones aza-michael, empleando hidrazidas n,n\u00c2\u00bf-disustituidas o hidrazonas derivadas del piruvaldeh\u00eddo con aldeh\u00eddos -insaturados. Adem\u00e1s, la versatilidad sint\u00e9tica de los aductos obtenidos ha permitido llevar a cabo su posterior derivatizaci\u00f3n, pudi\u00e9ndose destacar la s\u00edntesis de pirazolinas, pirazolidinonas y 1,3-diaminas.Por otro lado, tambi\u00e9n se ha demostrado la capacidad de las hidrazonas para actuar como nucle\u00f3filos carbonados en reacciones de adici\u00f3n conjugada. En este sentido, se ha estudiado la reacci\u00f3n de adici\u00f3n conjugada de hidrazonas n-monosustituidas a diferentes enales bajo activaci\u00f3n via iminio, observando que las hidrazonas que contienen un grupo electr\u00f3n atractor en la posici\u00f3n azomet\u00ednica son las m\u00e1s adecuadas para llevar a cabo este proceso. Adem\u00e1s, la actuaci\u00f3n de estas hidrazonas como equivalentes sint\u00e9ticos de aniones acilo se ha resaltado mediante la s\u00edntesis de compuestos 1,4-dicarbon\u00edlicos.Laburpenadoktorego tesi honetan, interes handiko zenbait konposatuen sintesi asimetrikoa aurrera eramateko estrategiak bildu dira. Etekin eta kontrol estereokimiko altuko prozesuak lortzeko, aminokatalizatzaileetan oinarritutako katalisia aukeratu da, sustratua iminio ioi kirala bihurtuz. Zentzu honetan, hidrazida eta hidrazonak adizio konjokatuetan, eta aktibazio mota honekin, erabil daitezken konposatuak direla frogatu da.Lehenik, hidrazida eta hidrazonen erabilera aztertu da nitrogenodun nukleozale gisa. Horretarako, bi aza-michael erreakzio ikertu dira hidrazida n,n\u00c2\u00bf-diordezkatuak edo pirubaldehidotik deribatutako hidrazonak eta aldehido ,-asegabetuk erabiliz. Era berean, lortutako aduktuen aldakortasun sintetikoak zenbait eraldaketa kimiko aurrera eramatea ahalbidetu du, garrantzi handiko zenbait konposatuen sintesia lortuz, hala nola, pirazolinak, pirazolidinonak edo 1,3-diaminak.Bestale, hidrazonen erabilera karbonodun nukleozale gisa ere frogatu da, erreakzio mota berdinerako. Horretarako, hidrazona n-monoordezkatuen adizio konjokatua enalekin aztertu da, azometino posizioan talde elektroi erakarle bat duten hidrazonek prozesu honetarako hoberenak direla ikuziz. Gainera, metodolog\u00eda honetan hidrazonek azil anioien ekibalente sintetiko gisa jokatzen dutela erakutsi da konposatu 1,4-dikarbonilikoak lortuz.<\/p>\n<p>&nbsp;<\/p>\n<h3>Datos acad\u00e9micos de la tesis doctoral \u00ab<strong>Hydrazides and hydrazones as versatile michael-donors for iminium-catalyzed conjugate addition reactions<\/strong>\u00ab<\/h3>\n<ul>\n<li><strong>T\u00edtulo de la tesis:<\/strong>\u00a0 Hydrazides and hydrazones as versatile michael-donors for iminium-catalyzed conjugate addition reactions <\/li>\n<li><strong>Autor:<\/strong>\u00a0 Maitane Fernandez Chento <\/li>\n<li><strong>Universidad:<\/strong>\u00a0 Pa\u00eds vasco\/euskal herriko unibertsitatea<\/li>\n<li><strong>Fecha de lectura de la tesis:<\/strong>\u00a0 25\/09\/2012<\/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>Efraim Reyes Mart\u00edn<\/li>\n<\/ul>\n<\/li>\n<li><strong>Tribunal<\/strong>\n<ul>\n<li>Presidente del tribunal: Jos\u00e9 Luis Garc\u00eda ruano <\/li>\n<li>darren Dixon &#8212; (vocal)<\/li>\n<li>alfonso Carlos Vald\u00e9s g\u00f3mez (vocal)<\/li>\n<li>nuria Sotomayor anduiza (vocal)<\/li>\n<\/ul>\n<\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n","protected":false},"excerpt":{"rendered":"<p>Tesis doctoral de Maitane Fernandez Chento Abstractin the work compiled in this thesis is presented a series of strategies that [&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":[1412,239,6775,12909],"tags":[201282,224953,122359,5621,224952,145676],"class_list":["post-113225","post","type-post","status-publish","format-standard","hentry","category-compuestos-heterociclicos","category-mecanismos-de-las-reacciones-organicas","category-organometalicos","category-pais-vasco-euskal-herriko-unibertsitatea","tag-alfonso-carlos-valdes-gomez","tag-darren-dixon","tag-efraim-reyes-martin","tag-jose-luis-garcia-ruano","tag-maitane-fernandez-chento","tag-nuria-sotomayor-anduiza"],"_links":{"self":[{"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/posts\/113225","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=113225"}],"version-history":[{"count":0,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/posts\/113225\/revisions"}],"wp:attachment":[{"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/media?parent=113225"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/categories?post=113225"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/tags?post=113225"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}