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Research Collection Research Collection Doctoral Thesis Synthesis and Properties of Acylphosphines Author(s): Schrader, Erik Publication Date: 2018 Permanent Link: https://doi.org/10.3929/ethz-b-000280388 Rights / License: In Copyright - Non-Commercial Use Permitted This page was generated automatically upon download from the ETH Zurich Research Collection. For more information please consult the Terms of use. ETH Library DISS. ETH NO. 25041 Synthesis and Properties of Acylphosphines A thesis submitted to attain the degree of DOCTOR OF SCIENCES of ETH ZURICH (Dr. sc. ETH Zurich) presented by ERIK SCHRADER MSc ETH (Chemistry), ETH Zurich born on 26.01.1990 citizen of Germany accepted on the recommendation of Prof. Dr. Hansjörg Grützmacher Prof. Dr. Antonio Togni 2018 “So once you do know what the question actually is, you’ll know what the answer means.” Douglas Adams Acknowledgements This work would not have been possible without the help and support of a lot of people. First and foremost I am very thankful, that Prof. Dr. Hansjörg Grützmacher allowed me to perform my PhD studies in his group. I was able to overcome some rough patches in different projects through his support and constant encouragement and when results came through, he was able to further unlock their potential. I would also like to thank Prof. Dr. Antonio Togni – not only for being my co-examiner, but also for giving me the opportunity to get a taste of teaching chemistry during my Masters studies as a teaching assistant in his lecture. Special thanks goes to my two mentors, who taught me the tricks of the trade in a chemical laboratory: Dr. Aaron Tondreau and Dr. Riccardo Suter. Without these two, the chemistry presented in this thesis would not have been achieved. Without Dr. Suter a lot of days in the lab would not have been as enjoyable and the evenings would have been much more dull. He is also credited with performing the DTF-calculations in Chapter 4 and proofreading a lot of this thesis. Dr. Michael Wörle of the Small Molecule Crystallography Center at ETH Zurich has contributed immensely to this work, not only by helping with difficult structures but also by keeping everything up and running and giving the freedom to measure crystals, that maybe were not perfect all the time. The same holds true for Dr. René Verel and Matt Baker, who were always helping with NMR-related problems or fixing the machines, when they could not cope with the workload. A big thank you goes to all members of the Grützmacher group, which supported me during the years: First of all – Christine Rüegg, whithout whom the whole group likely would have been disbanded by now. I was also very glad to have the support of other group members, such as Dr. Mark Bispinghoff, Dr. Robert Gilliard, Dr. Jaap Borger, Dr. Thomas Gianetti, Bruno Pribanic, Johanna Scoul, Fabian Müller, Jan Bloch, Andreas Beil, Riccardo Conti and Pascal Jurt. I would like to thank my students Jacqueline Waldvogel, Grégoire le Corré, Lukas Wassermann, Yannick Kürsteiner and Stefan Banz, for doing what I could not or did not want to do. My collaborators in the Kovalenko group, Georgian Nedelcu and Andriy Stelmakh, contributed to important part of this project and allowed to give fundamental studies a fascinating application. An important part of my time at ETH were my friends, who went to lunch with me on countless occassions. They were an unending source of morale, sometimes simply due to the fact, that others had it as bad me… In the end, I want to thank my family. Without my parents and grandparents, I would not be where I am today. They supported me the whole time and gave me the freedom and confidence to pursue the path I wanted to take. I am very grateful to my partner Andrea, who always supported me and gave me a place to come home to, where chemistry did not matter for a while. Table of Contents TABLE OF CONTENTS ........................................................................................................................................ 7 ABSTRACT ...................................................................................................................................................... 11 ZUSAMMENFASSUNG .................................................................................................................................... 15 PRECEEDING REMARKS .................................................................................................................................. 19 1 INTRODUCTION .................................................................................................................................... 21 1.1 SYNTHESIS OF ACYLPHOSPHINES ..................................................................................................................... 21 1.2 PROPERTIES OF ACYLPHOSPHINES ................................................................................................................... 22 1.3 THE PHOSPHORUS-ACYL BOND ...................................................................................................................... 24 1.4 AIM OF THIS THESIS ..................................................................................................................................... 25 2 SYNTHESIS OF PRIMARY ACYLPHOSPHINES BASED ON THE REACTION OF SODIUM DIHYDROPHOSPHIDE WITH ORGANIC ESTERS .................................................................................................................................. 27 2.1 INTRODUCTION ........................................................................................................................................... 27 2.2 AIM OF THIS PROJECT ................................................................................................................................... 30 2.3 RESULTS AND DISCUSSION ............................................................................................................................. 30 2.4 SUMMARY AND OUTLOOK ............................................................................................................................. 37 3 REACTIVITY OF MESITOYLPHOSPHINE .................................................................................................. 39 3.1 INTRODUCTION ........................................................................................................................................... 39 3.1.1 The Phospha-Michael Addition ..................................................................................................... 39 3.1.2 Synthesis of Diphosphenes ............................................................................................................ 40 3.2 AIM OF THIS WORK ...................................................................................................................................... 42 3.3 RESULTS AND DISCUSSION ............................................................................................................................. 43 3.3.1 Phospha-Michael Addition ............................................................................................................ 43 3.3.2 Synthesis of Diphosphenes ............................................................................................................ 47 3.4 SUMMARY AND OUTLOOK ............................................................................................................................. 53 4 SYNTHESIS OF MONO(ACYL)PHOSPHOLE OXIDES ................................................................................. 55 4.1 INTRODUCTION ........................................................................................................................................... 55 4.2 AIM OF THIS WORK ...................................................................................................................................... 57 4.3 RESULTS AND DISCUSSION ............................................................................................................................. 58 4.4 CONCLUSION AND OUTLOOK ......................................................................................................................... 64 5 SYNTHESIS OF TETRAKIS(ACYL)DIPHOSPHINES ..................................................................................... 65 5.1 INTRODUCTION ........................................................................................................................................... 65 5.2 AIM OF THIS WORK ...................................................................................................................................... 67 5.3 RESULTS AND DISCUSSION ............................................................................................................................. 67 5.4 SUMMARY AND CONCLUSION ........................................................................................................................ 72 6 SYNTHESIS OF TRIS(ACYL)- AND TRIS(CARBAMOYL)PHOSPHINES ......................................................... 75 6.1 INTRODUCTION ........................................................................................................................................... 75 6.2 AIM OF THIS PROJECT ................................................................................................................................... 79 6.3 RESULTS AND DISCUSSION ............................................................................................................................. 79 6.4 CONCLUSION AND OUTLOOK ........................................................................................................................
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