1.2. Alternative Solvents 2 1.3. Biomass and Lignin 4 1.4. Valorisation of Lignin 6

Table of Contents

Chapter 1: General Introduction 1 1.1. Sustainable Chemistry 1

1.2. Alternative Solvents 2 1.3. Biomass and Lignin 4 1.4. Valorisation of Lignin 6

1.5. Vanadium Triphenolamines 8 1.5.1. Synthesis 8

1.5.2. TPA metal complexes 9 1.5.3. VO-TPAs 10

1.6. Aim of the Thesis 12 1.7. References 13

Chapter 2: Mechanistic Study 17

2.1. State of the Art: Elucidations of Vicinal Diol C-C cleavages 18 2.1.1. Periodates and Pb(AcO)4 18

2.1.2. Silver catalysts 19 2.1.3. Iron catalysts 19 2.1.4. Cerium catalysts 20 2.1.5. Cobalt catalysts 21

2.1.6. Manganese catalysts 21

2.1.7. Palladium and Ruthenium catalysts 22 2.1.8. Molybdenum catalysts 22

2.1.9. Vanadium catalysts 23

2.2. Results and Discussion 27

2.2.1. Preliminary insights 27

2.2.2. Preliminary computational analysis 31 2.2.3. Kinetic analysis 33

2.2.4. MS analysis 35

2.2.5. Substrates with better leaving groups and

O scrambling 42

2.2.6. Kinetic isotope effects 44

2.2.7. Multi-parametric correlations 46 2.2.8. Linear free energy correlations 50 2.2.9. Computational studies 51

2.2.10. EPR studies on reduced V(III) and V(IV) Species 53 2.3. Conclusions 63

2.4. Experimental 65 2.5. References 75

Chapter 3: Aerobic Oxidative Cleavage in Aqueous Media 77 3.1. State of the Art: Micellar Catalysis 79

3.1.1. Structural characteristics of micelles 79 3.1.2. Catalytic reactions in micellar media 83 3.2. Results and Discussion 90

3.2.1. Incorporation studies 91

3.2.2. Selection of the conditions 92 3.2.3. Substrate scope 94

3.2.4. Scaling up 97

3.2.5. Improving recyclability 98

3.3. Conclusions 103 3.4. Experimental 104 3.5. References 114

Abbreviations 117

Acknowledgements 121