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  • The synthesis and application of bulky S- stereogenic and P- stereogenic

    chiral ligands Seán Doran

    ADVERTIMENT. La consulta d’aquesta tesi queda condicionada a l’acceptació de les següents condicions d'ús: La difusió d’aquesta tesi per mitjà del servei TDX (www.tdx.cat) ha estat autoritzada pels titulars dels drets de propietat intel·lectual únicament per a usos privats emmarcats en activitats d’investigació i docència. No s’autoritza la seva reproducció amb finalitats de lucre ni la seva difusió i posada a disposició des d’un lloc aliè al servei TDX. No s’autoritza la presentació del seu contingut en una finestra o marc aliè a TDX (framing). Aquesta reserva de drets afecta tant al resum de presentació de la tesi com als seus continguts. En la utilització o cita de parts de la tesi és obligat indicar el nom de la persona autora.

    ADVERTENCIA. La consulta de esta tesis queda condicionada a la aceptación de las siguientes condiciones de uso: La difusión de esta tesis por medio del servicio TDR (www.tdx.cat) ha sido autorizada por los titulares de los derechos de propiedad intelectual únicamente para usos privados enmarcados en actividades de investigación y docencia. No se autoriza su reproducción con finalidades de lucro ni su difusión y puesta a disposición desde un sitio ajeno al servicio TDR. No se autoriza la presentación de su contenido en una ventana o marco ajeno a TDR (framing). Esta reserva de derechos afecta tanto al resumen de presentación de la tesis como a sus contenidos. En la utilización o cita de partes de la tesis es obligado indicar el nombre de la persona autora.

    WARNING. On having consulted this thesis you’re accepting the following use conditions: Spreading this thesis by the TDX (www.tdx.cat) service has been authorized by the titular of the intellectual property rights only for private uses placed in investigation and teaching activities. Reproduction with lucrative aims is not authorized neither its spreading and availability from a site foreign to the TDX service. Introducing its content in a window or frame foreign to the TDX service is not authorized (framing). This rights affect to the presentation summary of the thesis as well as to its contents. In the using or citation of parts of the thesis it’s obliged to indicate the name of the author.

  • The synthesis and application of bulky S-

    stereogenic and P- stereogenic chiral

    ligands

    Seán Doran

    Facultad de Química

    Departamento de Química Orgánica

    Programa de doctorado: Química Orgánica Bienio 2010-2012

    Director de tesis: Xavier Verdaguer Espaulella

  • Memoria presentada por Seán Doran para optar al grado de doctor por la Universitat de

    Barcelona.

    Seán Doran

    Revisada por:

    Dr. Xavier Verdaguer Espaulella

    Barcelona, Octubre de 2012

  • Este trabajo se ha realizado con el soporte económico de la Obra Social “La Caixa” (becas

    pre-doctorales). El trabajo ha sido financiado mediante el proyecto de investigación MEC

    (CTQ 2008-00763), MICINN (CTQ2011-23620) y DGR (SGR-2009-00901).

    El trabajo experimental se ha llevado a cabo en el laboratorio de la Unitat de Recerca en

    Síntesi Asimètrica (URSA) del Institut de Recerca Biomèdica de Barcelona (IRB Barcelona),

    ubicado en el Parc Científic de Barcelona.

  • Acknowledgements

    First of all I would like to thank Prof. Antoni Riera for not only giving me the opportunity to

    carry out my doctoral thesis in his lab but also to completely transport my life from Ireland to

    beautiful Barcelona. Moving to Barcelona and Catalunya was the best decision I ever made

    in my life and it was your acceptance of me into the lab, Toni which made it possible so thank

    you so much. I want to of course thank my thesis supervisor Prof. Xavier Verdaguer for all

    the guidance, advice and help down through the years. You were available when I wasn’t

    sure what to do or where to go next but I was always granted the freedom and independence

    to investigate and explore as I wished for which I was always very appreciative.

    I want to thank everyone in the lab whoever gave me a hand with whatever bit of chemistry I

    was carrying out or equally as important, whoever made the lab a bit more craic to work in.

    To start off with I’ll have to thank (and of course I want to) the one and only Thierry Achard.

    You really helped me settle in at first, teaching me all about PNSO ligands, phosphines,

    rhodium and of course, for those first few nights out watching champions league with some

    Guinness in the Michael Collins before I knew anybody so thanks for that! I want to thank

    Marc Revés, you were always there to give a few pointers here and there especially in the

    beginning. I’ll thank Pablo my personal Spanish teacher (aunque mi español ha empeorado

    bastante ultimamente ya que lleva mil años en usa el muy berretes). I’ll thank Ana Vazquez,

    she was always there to give a hand, I might have only understood about half of what you

    were saying in the beginning (if that) but I loved hearing it! I’ll say thanks to Núria for being

    the bestest hoodie ever! Thanks to Yi-Ning for your ever-present beaming shining positivity!

    Thanks to Thierry León (what do you think about my... yeah!) for making the lab a wee bit

    more interesting! Thanks to A.. A... Alex for keeping the line in such pristine crystal

    cleanliness at all times! And the dry-box! Thanks to Edgarrrr for all that awesome

    hydrogenation time! I want to thank Cati Ferrer, Jean-Claude and Agustí Lledó for all their

    help. Of course I can’t forget in my thanks the frenchie Helea and hippi Silvia (hey soy Seán

    tio!). I’ll give a nod and a wink to the big Dan man, otherwise known as Super-Dan, the best

    signing Toni ever made! And a big, big thanks to all you guys for helping me with the Spanish

    summary - Núria, Edgar, Silvia, Alex and Álvaro!!!

    I want to give special thanks to Clara Caminal for her kind attention and help, whenever it

    was needed throughout the whole process of the PhD. As well I would thank Patricia Nadal,

  • Maria Rovira and Silvia Aguadé for every bit of help and attention you gave through all the

    bureaucratic intricacies that needed to be solved.

    I would thank the three members of my TAC committee Rodolfo Lavilla, Albert Moyano and

    Guillermo Müller for their help, advice and attention throughout the TAC proceedings. I

    would like to thank everybody from the Mass Spec facility for their work and contribution,

    past and present, Marta Vilaseca, Núria Omeñaca, Claudio Diema, Mar Vilanova and

    Marina Gay. I would give my thanks to everybody in the NMR unit in the Parc Científic and

    in UB for their help and contribution namely, Miguel Feliz, Maria Antònia Molins, Vicky

    Muñoz-Torero and Francisco Cárdenas. I would say thank you to Montse Alcón, Ester and

    Belen from Enantia for all their work on the chiral HPLC separations. Thanks should go

    Eduardo Carmelo Escudero for his work on the X-ray diffraction structures of the complexes

    shown here in this work.

    I would say a big thanks to all the great friends I have made here in the IRB down throughout

    the short few years I’ve spent here, to Peter, to Andrey, to Michael, to Marta, Özgen, Arjen,

    Anna-Iris and Gonzalo (the beer festival organizer!) To every single Brutal/ Soft and fluffy

    Deluxer a heads up and a cheers.

    A big special thank you and a kiss to Kader for all her love. A massive hug to my brothers

    Paddy and James who I miss so much and to all my friends who I wish I could spend more

    time with, Damian, Ross, Brendan, Jamie...and Tommy as well.

    And of course to my lovely Mum and my dear old Dad, this thesis is dedicated to you and you

    alone for you are the main reason it has been possible. Thank you for all your support in

    every sense and all your patience. I owe you everything.

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  • Content

    List of abbreviations

    Chapter 1 Introduction and objectives 3

    Chapter 2 Background 13

    Chapter 3 N-Phosphino sulfinamide ligands 57

    Chapter 4 P*-aminophosphine ligands 81

    Chapter 5 MaxPHOS and asymmetric hydrogenation 115

    Chapter 6 Conclusions 141

    Chapter 7 Experimental 145

    Chapter 8 1H and 13C NMR spectra

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