Novel sulfur-containing electrophiles in asymmetric organocatalysis [Elektronische Ressource] / vorgelegt von Krzysztof Hoffman

Informations

• Publié par: rheinisch-westfalischen_technischen_hochschule_-rwth-_aachen
• Publié le: 01 janvier 2008
• Nombre de lectures: 11
• Poids de l'ouvrage: 38 Mo

Extrait

Diese Dissertation ist auf den Internetseiten der Hochschulbibliothek online verfügbar.To my family.Table of contents
1. INTRODUCTION.......................................................................................... 1
1.1 Asymmetric Organocatalysis.............................................................................................1
1.1.1 Lewis Base Catalysis .......................................................................................................3
1.1.2 Lewis Acid ........................................................................................................9
1.1.3 Brønsted Base Catalysis..................................................................................................9
1.1.4 Acid.................................................................................................10
1.1.5 Bifunctional Organocatalysis..........................................................................................11
1.1.6 Combination of Transition-metal and Organocatalysis ..................................................14
1.2 Sulfur-Containing Electrophiles in Asymmetric Organocatalysis ...............................17
1.3 Sulfonic Acids ...................................................................................................................20
1.3.1 Asymmetric Synthesis of Sulfonic Acid Derivatives .......................................................21
1.3.2 Chiral Pool.....................................................................................................28
1.4 Objectives..........................................................................................................................31
2. RESULTS AND DISCUSSION .................................................................. 33
2.1 Thioalkylation of Carbonyl Compounds – The Concept ...............................................33
2.1.1 Preparation of Starting Materials ...................................................................................34
2.1.2 of Chiral Organocatalysts ...........................................................................38
2.1.3 Organocatalyzed Reactions with α-Chlorosulfides ........................................................41
2.1.4 Metal Catalyzed with α..........................................................50
2.1.5 Catalytic α-Phenylthiomethylation with S,N-Acetales ....................................................54
2.2 Organocatalyzed Michael-additions to α, β-Unsaturated Sulfonates – The Concept..57
2.2.1 Preparation of Starting Materials. ..................................................................................57
2.2.2 of Chiral Bifunctional Organocatalysts .......................................................60
2.2.3 Sulfa-Michael Addition to α,β-Unsaturated Sulfonates ..................................................65
2.2.4 Hydrogen Bonding to the Sulfonate ...............................................................................70
2.2.5 Diastereoselective Phospha-Michael Additions to α,β-Unsaturated Sulfonates ............71
3. CONCLUSIONS AND OUTLOOK............................................................. 73
3.1 Conclusions....................................................................................................................... 73
3.2 Outlook............................................................................................................................... 75
4. EXPERIMENTAL SECTION ...................................................................... 77
4.1 General Remarks............................................................................................................... 77
4.1.1 Solvents .........................................................................................................................77
4.1.2 Chemicals ......................................................................................................................77
4.2 General Procedures (GP) .................................................................................................78
4.2.1 GP 1: Preparation of Sulfides ........................................................................................78
4.2.2 GP 2: Chlorination with NCS.........................................................................................78Table of contents
4.2.3 GP 3: Enamine Catalyzed Reactions with α-Chlorosulfides ..........................................78
4.2.4 GP 4: Reactions of β-Keto Esters with α-Chlorosulfides................................................ 79
4.2.5 GP 5: Metal-Catalyzed Reactions with α-Chlorosulfides ...............................................79
4.2.6 GP 6: Reactions with Methylthiophenyl Amines ............................................................79
4.2.7 GP 7: Preparation of Methylsulfonates ..........................................................................79
4.2.8 GP 8: Synthesis of (Diethoxyphosphoryl)methanesulfonates........................................80
4.2.9 GP 9: of (E)-1-Alkenyl Sulfonates .................................................................80
4.2.10 GP 10: SMA to α,β-unsaturated sulfonates ...................................................................80
4.3 Reactions with α-Chlorosulfides .....................................................................................81
4.4 with Methylthiophenyl Amines ......................................................................85
4.5 Synthesis of (E)-1-Alkenyl Sulfonates ............................................................................88
4.6 Sulfa-Michael Addition to α,β-Unsaturated Sulfonates .................................................98
4.7 Synthesis of Chiral Organocatalysts112
5. APPENDIX............................................................................................... 116
5.1 List of Abbreviations ......................................................................................................116
6. REFERENCES......................... 119Introduction
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