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Digging Into Gold(I) Catalysis: Silver and Counterion Effects and Total Synthesis of Nardoaristolone B

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Digging Into Gold(I) Catalysis: Silver and Counterion Effects and Total Synthesis of Nardoaristolone B DIGGING INTO GOLD(I) CATALYSIS: SILVER AND COUNTERION EFFECTS AND TOTAL SYNTHESIS OF NARDOARISTOLONE B. Anna Homs i Riba Dipòsit Legal: T 1605-2015 ADVERTIMENT. L'accés als continguts d'aquesta tesi doctoral i la seva utilització ha de respectar els drets de la persona autora. Pot ser utilitzada per a consulta o estudi personal, així com en activitats o materials d'investigació i docència en els termes establerts a l'art. 32 del Text Refós de la Llei de Propietat Intel·lectual (RDL 1/1996). Per altres utilitzacions es requereix l'autorització prèvia i expressa de la persona autora. En qualsevol cas, en la utilització dels seus continguts caldrà indicar de forma clara el nom i cognoms de la persona autora i el títol de la tesi doctoral. No s'autoritza la seva reproducció o altres formes d'explotació efectuades amb finalitats de lucre ni la seva comunicació pública des d'un lloc aliè al servei TDX. Tampoc s'autoritza la presentació del seu contingut en una finestra o marc aliè a TDX (framing). Aquesta reserva de drets afecta tant als continguts de la tesi com als seus resums i índexs. ADVERTENCIA. El acceso a los contenidos de esta tesis doctoral y su utilización debe respetar los derechos de la persona autora. Puede ser utilizada para consulta o estudio personal, así como en actividades o materiales de investigación y docencia en los términos establecidos en el art. 32 del Texto Refundido de la Ley de Propiedad Intelectual (RDL 1/1996). Para otros usos se requiere la autorización previa y expresa de la persona autora. En cualquier caso, en la utilización de sus contenidos se deberá indicar de forma clara el nombre y apellidos de la persona autora y el título de la tesis doctoral. No se autoriza su reproducción u otras formas de explotación efectuadas con fines lucrativos ni su comunicación pública desde un sitio ajeno al servicio TDR. Tampoco se autoriza la presentación de su contenido en una ventana o marco ajeno a TDR (framing). Esta reserva de derechos afecta tanto al contenido de la tesis como a sus resúmenes e índices. WARNING. Access to the contents of this doctoral thesis and its use must respect the rights of the author. It can be used for reference or private study, as well as research and learning activities or materials in the terms established by the 32nd article of the Spanish Consolidated Copyright Act (RDL 1/1996). Express and previous authorization of the author is required for any other uses. In any case, when using its content, full name of the author and title of the thesis must be clearly indicated. Reproduction or other forms of for profit use or public communication from outside TDX service is not allowed. Presentation of its content in a window or frame external to TDX (framing) is not authorized either. These rights affect both the content of the thesis and its abstracts and indexes. Anna Homs i Riba Digging into Gold(I) Catalysis: Silver and Counterion Effects and Total Synthesis of Nardoaristolone B DOCTORAL THESIS Supervised by Prof. Antonio M. Echavarren Institut Català d’Investigació Química (ICIQ) Tarragona 2015 UNIVERSITAT ROVIRA I VIRGILI DEPARTAMENT DE QUIMICA ANALITICA I QUIMICA ORGANICA C/ Marcel.lí Domingo s/n Campus Sescelades 43007 Tarragona Tel. 34 977 55 97 69 Fax 34 977 55 84 46 e-mail: [email protected] FAIG CONSTAR que aquest treball, titulat “Digging into Gold(I) Catalysis: Silver and Counterion Effects and Total Synthesis of Nardoaristolone B”, que presenta Anna Homs i Riba per a l’obtenció del títol de Doctor, ha estat realitzat sota la meva direcció a l'Institut Català d'Investigació Química i que acompleix els requeriments per poder optar a Menció Internacional. Tarragona, 26 de novembre de 2014 El director de la tesi doctoral Antonio M. Echavarren Pablos [ A la meva família i a l’Edu En solitud, però no solitaris, reconduïm la vida amb la certesa que cap esforç no cau en terra eixorca. Dia vindrà que algú beurà a mans plenes l’aigua de llum que brolli de les pedres d’aquest temps nou que ara esculpim nosaltres. Miquel Martí i Pol Aquesta tesi doctoral s’ha dut a terme a l’Institut Català d’Investigació Química i ha estat supervisada pel Prof. Antonio M. Echavarren, a qui agraeixo la confiança depositada en mi des del dia que vaig arribar. Així mateix, agraeixo totes les eines i idees que m’ha proporcionat per no deixar d’aprendre contínuament així com per haver-me concedit la beca predoctoral FPI (Formación de Profesorado Investigador, Ministerio de Economía y Competitividad). Part d’aquesta tesi ha estat finançada també per una beca predoctoral ICIQ. During these four years I spend three-months in Prof. Jin-Quan Yu’s lab at The Scripps Research Institute. Thanks for making me feel a member of the group since the day I arrived as well as all the trust in me. Especial menció també a dos dels puntals del grup; Sònia Gavaldà i Imma Escofet. Sou l’eficiència personificada facilitant totes aquelles tasques que sovint no són gens senzilles amb el valor afegit de fer-ho sempre amb un somriure a la cara. Gràcies de tot cor. Looots of thanks to all the friends I had the pleasure to share the lab with; Yahui Wang (chinese tree), Pilar Calleja (molts ànims a aquesta recta final), Ana Escribano (gracias!), Dr. Michael E. Muratore (for taking over the project, proofreading the manuscript and for your tremendous patince!), Dr. Beatrice Ranieri (you could have started your Post-Doc a bit earlier, though!) and Elena de Orbe. Un gràcies gegantí i molt especial a la Carla Obradors (ja doctora un cop aquesta tesi estigui a l’impremta) i l’Imma Escofet (una altra vegada) amb qui he anat forjant una vertadera amistat dia rere dia i ha estat un plaer compartir aquests 4 i 3 anys, respectivament. Thanks to all the labmates in labs 2.2, 2.3 and 2.10 from 2010 to 2014: Masha Kirillova, Bart Herlé, Núria Huguet, Dr. Paul McGonigal, Dr. David Leboeuf, Zhouting Rong, Araceli Fernández, Laura Amenós, Katya Smirnova, Anthony Pitaval, Dr. Francesco Camponovo, Dr. Óscar de Pablo, Xiang Yin, Dr. Tania Jiménez, Dr. Javier Carreras, Dr. Laura López, Dr. Lorena Riesgo, Dr. Riccarda Miller, Morgane Gaydou, Sofía Ferrer, Ruth Dorel, Madeleine Livendhal, Cristina García, Dr. José M. Muñoz, Ismael Arroyo, Rogelio Solorio, Nicolas Delpont and Lourdes Maestre. Agrair també a la unitat tècnica de l’ICIQ; espectrometria de masses, ressonància magnètica nuclear, unitat de cromatografia, unitat de cinètica i difracció de Raigs X. Gràcies també al David Pena per solucionar tots aquells problemes informàtics. Very special thanks to (just Dr.) Asraa Ziadi, the best flatmate one can ever have. The only thing I regret is not moving together earlier (although we might not have slept that much then). Gràcies al David Bastida, al Dr. Toni Moragas i al Dr. Josep Cornellà (merci per les idees i suggeriments durant la tesi) per amenitzar els divendres sovint difícils de passar i per les estones a l’Azu (amb Barça o sense). A la Berta Camafort, Toni Bautista, Xacobe C. Cambeiro, Míriam Sau i a una llista interminable de gent que ha passat per l’ICIQ. Thanks to Dr. Xiaochen Wang (感校), Dr. Navid Dastbaravardeh and Jian He from the Yu’s lab for helping me at any time and discovering San Diego together. To Anish, Denis and the pack Ennio and Rita, my flatmates in the US. Lots of thanks to Dr. Christian Borch, who I hope to see very soon! Gràcies als de la uni (grup “Mikiliterari...”), especialment a l’Àlex Espel, l’Eli Vilella i l’Albert de Aróstegui; perquè amb els seus sopars, viatges o Aplecs, plens d’ironia i sarcasme que tant m’agrada, hagin fet aquests 4 anys més planers. Merci als d’Igualada (o Aranjuez) per no deixar de preguntar com em va tot. I a la Gemma Ferrer, a qui prometo trucar molt més sovint. Agrair també al Toni Jorba i a la Glòria Marsal, qui m’ha alimentat durant més del 50% del doctorat. Gràcies a tota la meva immensa (en sentit literal i figurat) família; a l’àvia Quini i als avis Homs, per les seves visites fugaç a Tarragona que sempre acabaven amb un bon arròs. Gràcies al recolzament incondicional dels meus germans, que ha estat clau: a la Maria (i al David), qui no deixo d’admirar profundament cada dia que passa i de qui he intentat imitar el camí, al Pep, qui m’ha encomanat la seva energia desbordant i a la Marta, per fer-me sentir imprescindible (especialment els diumenges al vespre). Al Pep i Quim Mestres els quals de manera sorprenent i amb la seva curta edat, m’han fet tocar de peus a terra més que ningú. Gràcies al pare i a la mare; pel seu continu recolzament en totes les decisions que he pres; per creure i confiar en mi cegament facilitat-me al màxim totes les situacions. Amb vosaltres he après que si treballes, pots anar on vulguis. I finalment, gràcies a l’Edu, qui hauria estat guardonat amb el Nobel de la Paciència i Comprensió durant 4 anys (o potser 7) consecutius. Infinites gràcies per tot. At the moment of writing this thesis, the results presented herein have been published in: On the Silver Effect and the Formation of Chloride-Bridged Digold Complexes Anna Homs, Imma Escofet, Antonio M. Echavarren Org. Lett. 2013, 15, 5782–5785. Dissecting Anion Effects on Gold(I)-Catalyzed Intermolecular Cycloaddtions Anna Homs,+ Carla Obradors,+ David Leboeuf, Antonio M.
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