University of Groningen
Design of new aggregates for catalysis
Tosi, Filippo
DOI:
10.33612/diss.107814277
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Publication date: 2019
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Tosi, F. (2019). Design of new aggregates for catalysis. Rijksuniversiteit Groningen. https://doi.org/10.33612/diss.107814277
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Design of New Aggregates for
Catalysis
II
The work described in this thesis was carried out at the Stratingh
Institute for Chemistry, University of Groningen, The Netherlands.
This work was financially supported by the Netherlands Organization
for Scientific Research (NWO-CW, NWO-Top Grant).
Print: Ipskamp Printing, Enschede, the Netherlands
ISBN: 978-94-034-2146-9 (Printed Version)
III
Design of New Aggregates for Catalysis
Proefschrift
ter verkrijging van de graad van doctor aan de Rijksuniversiteit Groningen
op gezag van de
rector magnificus prof. dr. C. Wijmenga en volgens besluit van het College voor Promoties.
De openbare verdediging zal plaatsvinden op vrijdag 13 december 2019 om 12.45 uur
door
Filippo Tosi
geboren op 13 December 1991 in Milaan, Italië
IV Supervisor Prof. dr. B. L. Feringa Co-supervisor Dr. S. J. Wezenberg Beoordelingscommissie Prof. dr. B. de Bruin prof. dr. S. Harutyunyan Prof. dr. S. Otto
V
Table of Contents
Chapter 1
Introduction 1
1.1 Outline of the Introduction 2
1.2 Amphiphilic Molecules 3
1.3 Critical Packing Parameter 4
1.3.1 Aggregates Deriving from Self-Assembly of Amphiphiles 6
1.4 Reactivity 8
1.4.1 Catalysis in Micelles 9
1.4.2 Catalysis in Vesicles 13
1.4.3 Catalysis in Cubic Phases 17
1.5 Conclusions 18
1.6 Outline of This Thesis 19
1.7 References 20
1.8 General Experimental Details 22
Chapter 2
Reorganization from Metastable to Stable Aggregation States of
BINOL-derived Amphiphiles in Water 25
2.1 Introduction 26 2.2 Synthesis 28 2.3 Self-Assembly Investigation 29 2.4 Time-Dependent Self-Assembly 31 2.5 Conclusions 34 2.6 Contributions 34 2.7 Experimental Section 34 2.8 Synthetic Procedures 35 2.9 References 39
Chapter 3
Salen-Based Amphiphiles: Directing Self-Assembly in Water by Metal
Complexation 43
3.1 Introduction 44
3.2 Synthesis 44
3.3 Self-Assembly Behavior 46
3.4 Critical Packing Parameter 49
3.5 Conclusions 50
3.6 Contributions 51
3.7 Experimental Section 51
VI
3.9 Appendix 55
3.10 References 58
Chapter 4
Tuning the Twist in Self-Assembled Chiral Ribbons in Water 61
4.1 Introduction 62
4.2 Synthesis 63
4.3 Self-Assembly Behavior 64
4.4 Thermo-Responsiveness 67
4.5 Tuning of the Self-Assembly by Variation of e.e. 69
4.6 Anion-Responsiveness 72 4.7 Conclusions 74 4.8 Contributions 74 4.9 Experimental Section 74 4.10 Synthetic Procedure 75 4.11 References 75
Chapter 5
Towards New Catalytically Active Amphiphiles 79
Section I – BINOL-Based Amphiphiles for Catalysis 80
5.1.1 Introduction 80
5.1.2 Design 81
5.1.3 Synthesis 82
5.1.4 Attempts to Perform Self-Assembly 85
5.1.5 Conclusions 85
5.1.6 Contributions 85
5.1.7 Experimental Section 85
5.1.8 Synthetic Procedures 86
5.1.9 References 91
Section II – Salen-Based Amphiphiles for Catalysis 93
5.2.1 Introduction 93 5.2.2 Henry Reaction 94 5.2.3 Ring-Opening of Epoxides 96 5.2.4 Alkene Epoxidation 98 5.2.5 Conclusions 99 5.2.6 Contributions 100 5.2.7 Experimental Procedures 100 5.2.8 References 101
Chapter 6
Oxygen Activated, Palladium Nanoparticle Catalyzed, Ultrafast
Cross-Coupling of Organolithium Reagents 103
6.1 Introduction 104
6.2 Reaction Optimization 105
VII
6.4 Active Catalyst Investigation 107
6.5 Radioactive Cross-Coupling and Deuterium Labelling 116
6.6 Conclusions 118
6.7 Contributions 118
6.8 Experimental Procedures 118
6.9 References 124
Chapter 7
An Atom Efficient Synthesis of Tamoxifen 125
7.1 Introduction 126
7.2 Carbolithiation Optimization 127
7.3 Reaction Optimization 128
7.4 Tamoxifen Synthesis 130
7.5 Reaction Mass Efficiency 132
7.6 Conclusions 133 7.7 Contributions 133 7.8 Experimental Section 133 7.9 Synthetic Procedures 133 7.10 References 136 Summary 139 Samenvatting 142 Riassunto 145 Acknowledgements 149
