Iron-catalyzed reactions and the role of metal contaminants [Elektronische Ressource] / Julien Bonnamour

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Iron-Catalyzed Reactions and the Role of Metal Contaminants Julien Bonnamour Iron-Catalyzed Reactions and the Role of Metal Contaminants Von der Fakultät für Mathematik, Informatik und Naturwissenschaften der RWTH Aachen University zur Erlangung des akademischen Grades eines Doktors der Naturwissenschaften genehmigte Dissertation vorgelegt von Master of Science Julien Bonnamour aus Paris (France) Berichter: Universitätprofessor Dr. Carsten Bolm Universitätprofessor Dr. Dieter Enders Tag der mündlichen Prüfung: 26.08.2011 Diese Dissertation ist auf den Internetseiten der Hochschulbibliothek online verfügbar This thesis presents the work carried out at the Institute of Organic Chemistry of RWTH Aachen University between October 2007 and July 2011 under the supervision of Prof. Dr. Carsten Bolm. I would like to thank Prof. Dr. Carsten Bolm for giving me the opportunity to work in his group on this interesting research theme and also for the nice working atmosphere. I would like to thank also Prof. Dr. Dieter Enders for his kind assumption of the co-reference. Parts of this work have already been published: 1) J. Bonnamour, C. Bolm “Iron-Catalyzed Intramolecular O-Arylation: Synthesis of 2-Aryl Benzoxazoles” Organic Letters 2008, 10, 2665. 2) J. Bonnamour, C.

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Publié le 01 janvier 2011
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Iron-Catalyzed Reactions and the Role
of Metal Contaminants
















Julien Bonnamour





Iron-Catalyzed Reactions and the Role of Metal Contaminants




Von der Fakultät für Mathematik, Informatik und Naturwissenschaften der RWTH Aachen
University zur Erlangung des akademischen Grades eines Doktors der Naturwissenschaften
genehmigte Dissertation




vorgelegt von





Master of Science

Julien Bonnamour

aus Paris (France)








Berichter: Universitätprofessor Dr. Carsten Bolm
Universitätprofessor Dr. Dieter Enders


Tag der mündlichen Prüfung: 26.08.2011





Diese Dissertation ist auf den Internetseiten der Hochschulbibliothek online verfügbar





This thesis presents the work carried out at the Institute of Organic Chemistry of RWTH
Aachen University between October 2007 and July 2011 under the supervision of Prof. Dr.
Carsten Bolm.



I would like to thank Prof. Dr. Carsten Bolm for giving me the opportunity to work in his
group on this interesting research theme and also for the nice working atmosphere.

I would like to thank also Prof. Dr. Dieter Enders for his kind assumption of the co-reference.





Parts of this work have already been published:

1) J. Bonnamour, C. Bolm
“Iron-Catalyzed Intramolecular O-Arylation: Synthesis of 2-Aryl Benzoxazoles”
Organic Letters 2008, 10, 2665.

2) J. Bonnamour, C. Bolm
“Iron Salts in the Catalyzed Synthesis of 5-Substituted 1H-Tetrazoles”
Chemistry, a European Journal 2009, 15, 4543.

3) J. Bonnamour, M. Piedrafita, C. Bolm
“Iron and Copper Salts in the Synthesis of Benzo[b]furans”
Advanced Synthesis and Catalysis 2010, 352, 1577.

4) J. Bonnamour, C. Bolm
“Iron(II) Triflate as Catalyst for the Synthesis of Indoles by Intramolecular C-H
Amination”
Organic Letters 2011, 13, 2012.
Acknowledgments


First of all, I would like to thank my supervisor Prof. Dr. Carsten Bolm for giving me the
opportunity to work in his group, for optimal working conditions and additionally for his
enthusiastic interest in new results.

I thank the technical and administrative personnel of the Institute of Organic Chemistry
RWTH Aachen. A great thank to Mrs. Ingrid Voss for her kindness and her help with the
German administration. I would like to thank Rolf Winkels and Björn Dreindl for their
kindness and the technician Susi Grünebaum and Pierre Winandy for their help in the
preparation of starting materials.

I am really grateful to Arkaitz Correa for the guidance during the work on my thesis, his
humour and also for his Spanish omelet! I wish to thank for so many reasons Ankur Pandey
and Bernhard Füger that it would really be too long to mention here. My particular gratitude
goes to Johannes Johansson for proof-reading and for his very useful suggestions, comments
and much more. Thank you Maria Piedrafita for the fruitful collaboration.

I am thankful to Jenna Lynn Head, Nick Swisher and Ankur Pandey for proof-reading this
thesis.

I am grateful to the sportive people such as the swimmers: Arkaitz Correa, Maria Piedrafita,
Johannes Johansson, the professional ping-pong player Julien Buendia, and the basket team:
Johannes Johansson, Ankur Pandey and Lianghua Zou.

De sincères remerciements se dirigent vers Julien Buendia pour sa jovialité, sa convivialité,
ses connaissances et ses conseils avisés dans tous les domaines. Merci aussi à Mathieu Candy
pour son aide lors de la rédaction de la thèse.

Thanks to Seong Jun Park, Julien Buendia for the nice ambiance in the 5.06 lab.

I would like to thank all the AK Bolm for the nice atmosphere in the group.
谢 谢 to the amiable Chinese, Jia-Rong Chen, Xiao Yun Chen, Wanrong Dong, Hui-Jun
Zhang, Lianghua Zou, Long Wang, Sheng-Mei Lu, Zhen-Jiang Liu, who were always ready
to go out when a party was announced.

A special thank goes to Inna Schuller for her help during the preparation of this manuscript.
General Introduction 1
Iron in Cross-Coupling Reactions 3
1. Cross-Coupling 3
2. Palladium 3
3. Palladium versus Iron 4
4. History of Iron-Catalyzed Cross-Coupling Reactions 4
4.1. The Beginning of Iron Catalysis 4
4.2. Iron-Catalyzed Coupling with Grignard Reagents 5
4.3. Iron-Catalyzed Coupling Reactions without Grignard Reagents 8
4.3.1 Organocopper Reagents 8
4.3.2 Organomanganese Reagents 9
4.3.3 Organozinc Reagents 9
5. Iron-Catalyzed Reactions 10
5.1. Iron-Catalyzed Sonogashira-Hagihara Reaction 10
5.2. Sonogashira-Type Reaction 11
5.3. Coupling of Terminal Alkynes with Alcohols 11
5.4. Coupling Reaction with Three Components 12
5.5. Iron-Catalyzed Mirozoki-Heck Reaction 12
5.6. Iron-Catalyzed Suzuki-Miyaura Reaction 13
5.7. Iron-Catalyzed Arylation of Arene with Aryl Halides 13
5.8. Hydrogenation and Reduction 14
5.9. Cyclization Reaction 16
5.9.1. Prins Cyclization 16
5.9.2. Other Cyclizations 16
5.10. Oxidation 17
5.10.1. Oxidation of C-H Bond 17
5.10.2. Oxidation of Sulfur 18
5.11. Iron Salts and Metal Contaminants 19
5.12. Iron-Catalyzed Coupling Reactions 22
5.12.1. Iron-Catalyzed Intermolecular N-Arylation 22
5.12.2. Iron-Catalyzed Intermolecular S-Arylation 24
5.11.3. Iron-Catalyzed Intermolecular O-Arylation 25
6. Conclusion 25 Result and Discussion 27
I. Iron-Catalyzed Intramolecular O-Arylation 27
1. Benzoxazole 27
1.1. Introduction 27
1.2. Study of the Reaction 28
1.2.1. Influence of Temperature 28
1.2.2. Influence of Base 29
1.2.3. Influence of Solvent 29
1.2.4. Influence of Different Iron Salts and Ligands 30
1.3. Scope of the Reaction 31
2. Benzofuran 32
2.1. Introduction 32
2.2. Study of the Reaction 33
2.2.1. Influence of Base 33
2.2.2. Influence of Solvent 34
2.2.3. Influence of Ligand 35
2.2.4. Influence of the Purity of the Catalyst 35
2.3. Scope of the Reaction 37
II. Iron Salts in Click Chemistry 39
1. Introduction 39
2. Syntheses of 1,2,3-Triazoles 40
3. Synthesis of Tetrazoles 41
3.1. Introduction 41
3.2. Study of the Reaction 42
3.2.1. Influence of the Iron Source 42
3.2.2. Influence of the Azide 43
3.2.3. Influence of Temperature 43
3.2.4. Influence of Solvent 44
3.3. Scope of the Reaction 45
4. Conclusion 46
III. Iron(II) Triflate as Catalyst for the Synthesis of Indoles by Intramolecular
C-H Amination 47
1. Introduction 47 2. Study of the Reaction 48
2.1. Influence of Catalyst 49
2.2. Influence of Solvent 49
2.3. Influence of Copper 50
2.4. Influence of Temperature 50
3. Scope of the Reaction 51
4. Conclusion 52
Summary and Outlooks 53
Experimental Part 56
1. General Techniques 56
2. Solvents 56
3. Determination of the Physical Properties of the Synthesized Compounds 56
1
3.1. H NMR Spectroscopy 56
133.2. C NMR Spectroscopy 57
193.3. F NMR Spectroscopy 57
3.4. Mass Spectroscopy 57
3.5. GC-MS Measurements 57
3.6. Elemental Analysis 57
3.7. Melting Point 57
4. Chromatographic Methods 57
4.1. Preparative Column Chromatography 57
4.2. Thin Layer Chromatography (TLC) 58
5. Synthesis of 2-Aryl Benzoxazoles 58
6. Synthesis of Benzofurans 68
7. Synthesis of 5-Substituted 1H-Tetrazoles 81
8. Synthesis of Indoles 87
Appendix 102
List of Abbreviations 102