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Thesis Yahui Wang GOLD CARBENES FROM CYCLOHEPTATRIENES: GENERATION AND FATE. Yahui Wang Dipòsit Legal: T 1612-2015 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. Yahui Wang Gold Carbenes from Cycloheptatrienes: Generation and Fate DOCTORAL THESIS Supervised by Prof. Antonio M. Echavarren Institut Català d’Investigació Química (ICIQ) Tarragona 2014 2 Av. Països Catalans, 16 43007 Tarragona Tel. 977 920 218 Fax. 977 920 225 HAGO CONSTAR que este trabajo de investigación titulado “Gold Carbenes from Cycloheptatrienes: Generation and Fate”, que presenta Yahui Wang para la obtención del título de doctor, ha sido realizado bajo mi dirección en el Institut Català d’Investigació Química vinculado a la Universidad Rovira I Virgili. Tarragona, 14 de maig de 2014 El director de la Tesis Doctoral Prof. Antonio M. Echavarren 3 4 To my wife. 5 6 In gold we trust. 7 Acknowledgements The research documented in this Doctoral Thesis was carried out in l’Institut Català d’Investigació Química (ICIQ) under the supervision of Prof. Antonio M. Echavarren. I would like to thank Antonio for giving me so much guidance relating to this research and personal concerns in the nearly four years I have spent in his laboratory. I do thank Prof. Antonio M. Echavarren for performing the DFT calculations in this Thesis. I would like to thank the ICIQ foundation for the fellowships allocated to me during my Thesis (October 2010 - July 2014). I would also like to thank Sònia Gavaldà, Vanessa Martínez and Imma Escofet for their wonderful efforts, which allowed me to dedicate most of my time on research. Thanks to Dr. Verónica López-Carrillo, Dr. Juhanes Aydin, Dr. María Moreno, Dr. Timm Haug, Dr. Madeleine Livendahl, Dr. Riccardo Sinisi and especially Dr. César R. Solorio-Alvarado for taking care of me during my first month (homesick period) in Tarragona. I would like to thank all of my labmates, especially Katya Smirnova (Princess), Pilar Calleja, Anna Homs (Catalan Flower), Dr. Oscar Pablo, Dr. José M. Muñoz, Dr. Javier Carreras, Dr. Laura López, Dr. Núria Huguet, Dr. Beatrice Ranieri, Cristina Garcia, Elena Orbe-Izquierdo, Alba González, Sofia Ferrer, Bart Herlé and Dr. Anthony Pitaval (Big Daddy) who contributed to give this laboratory a friendly and happy atmosphere. I would like to thank Zhouting Rong, Bart Herlé, Dr. Michael Muratore and Dr. Paul McGonigal for pleasant collaboration in some projects. I would like to thank all of the smokers in the lab, Dr. Tania Jiménez, Morgane Gaydou, Masha Kirillova, Dr. David Leboeuf, Ruth Dorel (quitting now) and especially Carla Obradors (my Chemistry Model) for discussing chemistry during breaks we have taken together. I would like to thank Dr. Hamidreza Samouel and Juan Gallardo for discussing basic concepts in catalysis, and Carla Obradors, Dr. Tania Jiménez, Dr. Michael Muratore and Dr. Paul McGonigal for valuable suggestion and language help when preparing this Thesis. In addition, I would like to thank the ICIQ Research Support team for their availability and their help during my Thesis. 8 I would like to give huge and special thanks to Dr. Claudia De León (Boss), Dr. Michael Muratore and Dr. Paul McGonigal (Cherry-boy) for giving color to my life here. Thanks to all of the people who gave me help in these years in Tarragona. Finally, I would like to end up by thanking the most important people: my parents and my wife. 9 At the moment of the writing of this thesis, the results presented herein had been published in: “Intermolecular Reactions of Gold(I)-Carbenes with Furans by Related Mechanisms” David Lebœuf, Morgane Gaydou, Yahui Wang, and Antonio M. Echavarren, Org. Chem. Front. 2014, 1, DOI: 10.1039/c4qo00130c. “Formal (4+1) Cycloaddition of Methylencyclopropanes with 7-Aryl-1,3,5- cycloheptatrienes by Triple Gold(I) Catalysis” Yahui Wang, Michael E. Muratore, Zhouting Rong, and Antonio M. Echavarren, Angew. Chem. Int. Ed. 2014, 53, DOI: 10.1002/anie.201404029. “Gold(I) Carbenes by Retro-Buchner Reaction: Generation and Fate” Yahui Wang, Paul R. McGonigal, Bart Herlé, Maria Besora, and Antonio M. Echavarren, J. Am. Chem. Soc. 2014, 136, 801–809. “Gold for the Generation and Control of Fluxional Barbaralyl Cations” Paul R. McGonigal, Claudia de León, Yahui Wang, Anna Homs, César R. Solorio- Alvarado, and Antonio M. Echavarren, Angew. Chem. Int. Ed. 2012, 51, 13093– 13096. “Cyclopropanation with Gold(I) Carbenes by Retro-Buchner Reaction from Cycloheptatrienes” César R. Solorio-Alvarado, Yahui Wang, and Antonio M. Echavarren, J. Am. Chem. Soc. 2011, 133, 11952–11955. 10 Table of Contents Prólogo ...................................................................................................................... 13 List of Catalysts, Abbreviations and Acronyms ................................................... 14 Resumen ................................................................................................................... 15 General introduction ............................................................................................... 19 Singlet and triplet carbenes ................................................................................... 19 Fischer and Schrock carbenes ............................................................................... 19 Gold carbenes ....................................................................................................... 21 Methods for generating free carbenes .................................................................. 24 Generation of gold carbenes ................................................................................. 29 Buchner ring expansion ........................................................................................ 33 Retro-Buchner reactions ....................................................................................... 34 Chapter 1. The generation and fate of gold carbenes by retro-Buchner reactions ................................................................................................................... 37 Background ........................................................................................................... 37 Objectives ............................................................................................................. 38 Synthesis of 7-aryl cycloheptatrienes ................................................................... 39 Results and discussions. ....................................................................................... 41 Cyclopropanation ............................................................................................. 41 Kinetic study of cyclopropanation ................................................................... 43 DFT calculations of retro-Buchner reaction .................................................... 44 Cyclopropanation/Cope-rearrangement ..........................................................
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