Studies on transition metal catalysed oxidations with hydrogen peroxide as terminal oxidant [Elektronische Ressource] / vorgelegt von Chiara Pavan

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• Publié par: rheinisch-westfalischen_technischen_hochschule_-rwth-_aachen
• Publié le: 01 janvier 2005
• Nombre de lectures: 12
• Langue: English

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STUDIES ON TRANSITION METAL-CATALYSED OXIDATIONS WITH
HYDROGEN PEROXIDE AS TERMINAL OXIDANT













Chiara Pavan






STUDIES ON TRANSITION METAL-CATALYSED OXIDATIONS WITH
HYDROGEN PEROXIDE AS TERMINAL OXIDANT



Von der Fakultät für Mathematik, Informatik und Naturwissenschaften der Rheinisch-
Westfälischen Technischen Hochschule Aachen zur Erlangung des akademischen Grades
einer Doktorin der Naturwissenschaften genehmigte Dissertation



vorgelegt von

Chiara Pavan

aus Torino (Italien)


Berichter: Universitätsprofessor Dr. C. Bolm
Universitätsprofessor Dr. D. Enders




Tag der mündlichen Prüfung:
19.09.2005


Diese Dissertation ist auf den Internetseiten der Hochschulbibliothek online verfügbar.




The work here reported has been carried out at the Institute of Organic Chemistry of the
RWTH under the supervision of Prof. Dr. Carsten Bolm between October 2001 and January
2004.






Part of this work have been published:

1. Hydrocarbon oxidations with hydrogen peroxide catalyzed by a soluble polymer-bound
Manganese(IV) complex with 1,4,7-triazacyclononane. Galina V. Nizova, Carsten Bolm,
Simona Ceccarelli, Chiara Pavan, Georgiy B. Shul'pin, Adv. Synt. Cat. 2002, 344, 899.

2. Iron-catalyzed Oxidation of Cycloalkanes and Alkylarenes with H O . Chiara Pavan, Julien 2 2
Legros, Carsten Bolm, Adv. Synt. Cat. 2005, 347, 703.








I would like to thank Prof. Dr. C. Bolm for giving me the opportunity to work in his group,
for the stimulating research topic and for the exceptional working conditions.
I am very grateful to Prof. Dr. D. Enders for his kind assumption of the co-reference.

The art of losing isn’t hard to master;
so many things seem filled with the intent
to be lost that their loss is no disaster.

Lose something every day. Accept the fluster
of lost door keys, the hour badly spent.
The art of losing isn’t hard to master.

Then practice losing farther, losing farther:
places, and names, and where it was you meant
to travel. None of these will bring disaster.

I lost my mother’s watch. And look! my last, or
next-to-last, of three loved houses went.
The art of losing isn’t hard to master.

I lost two cities, lovely ones. And, vaster,
some realms I owned, two rivers, a continent.
I miss them, but it wasn’t a disaster.

--Even losing you (the joking voice, a gesture
I love) I shan’t have lied. It’s evident
the art of losing’s not too hard to master
though it may look like (Write it!) like disaster.

One Art by Elisabeth Bishop




To my family and friends

INDEX


1. Introduction 1
1.1 Oxidation Reactions: A Challenge 1
1.2 Hydrogen Peroxide: Production and Uses 2
2. Fe-Catalysed CH Activation of Hydrocarbons 5
2.1 Introduction 5
2.1.1 Alkane Oxidation 5
2.1.1.1 Biological Systems
2.1.1.2 Chemical Systems 7
2.2 Goal of the Study 14
2.3 Results and Discussion 15
2.3.1 Preliminary Experiments and Catalyst Optimisation 15
2.3.2 Optimisation of the Additive 17
2.3.3 Optimisation of the Catalyst Loading 20
2.3.4 of the Solvent System 21
2.3.5 Substrate Scope 22
2.3.6 In situ IRStudies 28
2.3.7 Studies of CH Activation in Ionic Liquids 32
2.3.8 Conclusion 35

3. Fe-Catalysed Oxidative Cleavage of Double Bonds 37
3.1 Introduction 37
3.1.1 Ozonolysis 38
3.1.2 Permanganate 40
3.1.3 Osmium Tetroxide and Sodium Periodate 40
3.1.4 Ruthenium-Catalysed Systems 42
3.1.5 Rhenium-Catalysed 43
3.1.6 Other Systems 44
3.2 Goal of the Study 45
3.3 Results and Discussion 47
3.3.1 Preliminary Experiments and Catalyst Optimisation 47
3.3.2 Substrate Scope 52
3.3.3 Proposed Mechanism 57
3.3.4 Conclusion 58
4. Studies towards the Enantioselective CH Activation with TACN 60
4.1 Introduction 60
4.1.1 Triazacyclononanes Complexes 60
4.1.2 Synthesis of Triazacyclononanes: General Approaches 62
4.1.3 Application of Metal-Triazacyclononanes Complexes 65
4.1.3.1 Mn-TACN Complexes Catalysed Epoxidations 65
4.1.3.2 Metal-TACN Complexes Catalysed CH Activation 70
4.2 Goal of the Study 72
4.3 Results and Discussion 73
4.3.1 Synthetic Strategy 74
4.3.2 Synthesis of Chiral C -Symmetric TACNs Derived from Amino Acids 76 1
4.3.2.1 Synthesis of Protected Amino Alcohols 76
4.3.2.2 Synthesis of N,N’-Dimethyldichloroamide
4.3.2.3 Synthesis of C-Symmetric Triazacyclononanes 77 1
4.3.3 Enantioselective CH Activation Studies 78
4.3.4 Epoxidation 81
4.4 Studies on the Asymmetric CH Activation Using Carboxylic Acids as
Chiral Promoters 82
4.5 Conclusion 85

5. Experimental Section 87
5.1 General Remarks
5.2 Solvents 87
5.3 Determination of the Physical Data 88
5.4 Chromatographic Methods 89
5.5 Fe-Catalysed CH Activation of Hydrocarbons 90
5.5.1 General Protocol for the Oxidation of Alkylarenes and Cycloalkanes 90
5.5.2 Oxidation of Cyclohexane: Experiments in CDCN 96 3
5.5.3 General Protocol for in situ IR Studies 97
5.5.4 General Protocol for the CH Activation in Ionic Liquids 98