Asymmetric aminocatalysis: Knoevenagel condensation, epoxidation of 2-cyclopentenones and alpha-alkylation of alpha-branched aldehydes
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| Format: | Thesis Book |
| Language: | English |
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2012
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| Online Access: | Inhaltsverzeichnis |
| Physical Description: | IX, 212 S. graph. Darst. |
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| 245 | 1 | 0 | |a Asymmetric aminocatalysis |b Knoevenagel condensation, epoxidation of 2-cyclopentenones and alpha-alkylation of alpha-branched aldehydes |c vorgelegt von Anna Lee |
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| 502 | |a Köln, Univ., Diss., 2012 | ||
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| _version_ | 1804149696082477056 |
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| adam_text | Titel: Asymmetric aminocatalysis
Autor: Lee, Anna
Jahr: 2012
Table of Contents
ABSTRACT......................................................................................................................V
LIST OF ABBREVIATIONS.......................................................................................VI
ACKNOWLEDGEMENTS..........................................................................................IX
1. INTRODUCTION.......................................................................................................1
2. BACKGROUND..........................................................................................................4
2.1. Asymmetric Organocatalysis....................................................................................4
2.1.1 Introduction.........................................................................................................................4
2.1.2 Classification of Modern Organocatalysis........................................................................6
2.1.3 Aminocatalysis.....................................................................................................................9
2.1.3.1 New Activation Modes...............................................................................................10
2.1.3.2 Asymmetric Counteranion-Directed Catalysis (ACDC).........................................13
2.1.3.3 Primary Amine Salt Catalysis...................................................................................14
2.1.3.4 Primary Amine Catalysts Based on Cinchona Alkaloids.......................................17
2.2 Kinetic and Dynamic- Kinetic Resolution .............................................................21
2.3 Catalytic Asymmetric Konevenagel Condensation Reaction ..............................23
2.3.1 Overview of Knoevenagel Condensation.........................................................................23
2.3.2 Stereoselective Knoevenagel Condensation....................................................................24
2.3.3 Limitations of the Knoevenagel Condensation...............................................................27
2.4 Catalytic Asymmetric Epoxidation of Olefins.......................................................30
2.4.1 Overview of Catalytic Asymmetric Epoxidation............................................................30
2.4.2 Weitz-Scheffer Epoxidation.............................................................................................31
2.4.3 Organocatalytic (Lewis Base) Approaches to Epoxidation...........................................35
2.4.4 Enantioselective Epoxidation of Cyclic a,fi-Unsaturated Ketones...............................39
2.4.5 Synthetic Utility of Epoxycyclopentanones.....................................................................41
2.5 Catalytic Asymmetric a-Alkyiation of Aldehydes.................................................43
2.5.1 Overview of Catalytic Asymmetric a-Alkylation...........................................................43
2.5.2 Aminocatalyzed a-Alkylation of Aldehydes via Sf/2 type Mechanism.........................44
2.5.3 Aminocatalyzed a-Alkylation of Aldehydes via S^l type Mechanism.........................48
2.5.4 a-Alkylation of Aldehydes via SOMO Catalysis.............................................................50
3. OBJECTIVES OF THIS PH.D. WORK.................................................................54
3.1 Development of a Catalytic Asymmetric Knoevenagel Condensation................54
3.2 Catalytic Asymmetric Epoxidation of 2-Cyclopentenones...................................55
3.3 Catalytic Asymmetric a-Alkylation of a-Branched Aldehydes............................56
4. RESULTS AND DISCUSSION................................................................................57
4.1 Catalytic Asymmetric Knoevenagel Condensation...............................................57
4.1.1. Identification of a Model System....................................................................................57
4.1.2 Catalyst Screening Experiments......................................................................................58
4.1.3 Optimization of the Reaction Parameters.......................................................................63
4.1.3.1 Solvent Screening Experiments.................................................................................63
4.1.3.2 Additives Screening Experiments.............................................................................64
4.1.4 Optimization of Reaction Conditions..............................................................................67
4.1.5 Optimization of the Reaction Temperature....................................................................69
4.1.6 Synthesis of Chiral Primary Amines Based on the Quinuclidine Scaffold..................70
4.1.7 Modification of Cinchona Based Catalysts.....................................................................74
4.1.8 Reaction Scope and Discussion........................................................................................81
4.1.8.1 Catalytic Asymmetric Knoevenagel Reaction Scope: Aldehydes..........................81
4.1.8.2 Catalytic Asymmetric Knoevenagel Reaction Scope: Malonates..........................82
4.1.8.3 Synthetic Utility of the Knoevenagel Condensation Products................................83
4.1.8.4 Reaction Limitations..................................................................................................86
4.2 Catalytic Asymmetric Epoxidation of 2-Cyclopentenones...................................88
4.2.1 Identification of a Model System.....................................................................................88
4.2.2 Optimization of the Reaction Parameters.......................................................................90
4.2.3 Reaction Scope...................................................................................................................95
4.2.4 Reaction Limitations.........................................................................................................99
4.3 Catalytic Asymmetric a-Alkylation of a-Branched Aldehydes..........................101
4.3.1 Screening Studies.............................................................................................................102
4.3.1.1 Identification of a Model System: Catalysts..........................................................102
4.3.1.2 Optimization of the Reaction Parameters..............................................................108
4.3.2 Catalytic System Optimization......................................................................................111
4.3.3 Reaction Scope and Discussion......................................................................................118
5. SUMMARY..............................................................................................................125
5.1 Catalytic Asymmetric Knoevenagel Condensation Reaction.............................125
5.2 Catalytic Asymmetric Epoxidation of 2-Cyclopentenones.................................126
5.3 Catalytic Asymmetric a-Alkylation of a-Branched Aldehydes..........................128
5.4 Synthesis of New Cinchona Derived Catalysts.....................................................129
6. OUTLOOK..............................................................................................................131
6.1 Epoxidation of a-Substituted 2-Cyclopentenones................................................131
6.2 Kinetic Resolution of 4-Substituted Cyclopent-2-enones....................................134
7. EXPERIMENTAL SECTION...............................................................................138
7.1 General Experimental Conditions.........................................................................138
7.2 Catalytic Asymmetric Knoevenagel Condensation.............................................141
7.2.1 Preparation of the Starting Materials...........................................................................141
7.2.2 General Knoevenagel Condensation Procedures.........................................................147
7.2.2.1 General Procedure for Racemates Preparation....................................................147
7.2.2.2 General Procedure for the Catalytic Asymmetric Knoevenagel Reaction..........148
7.2.2.3 Application of Asymmetric Knoevenagel Condensation Products......................157
7.2.2.4 Determination of the Absolute Configuration of 41a............................................158
7.2.3 Synthesis of Catalysts......................................................................................................159
7.2.3.1 Synthesis of Cinchona Alkaloid Derived Catalysts...............................................159
7.2.3.2 Synthesis of Novel Cinchona Alkaloid Derived Catalysts.....................................168
7.2.3.3 Synthesis of 2-(a-Aminobenzyl)quinuclidine.........................................................173
7.3 Catalytic Asymmetric Epoxidation of 2-Cyclopentenones.................................178
7.3.1 Preparation of the Starting Materials...........................................................................178
7.3.2 General Epoxidation Procedures...................................................................................181
7.3.2.1 General Procedure for Racemates Preparation....................................................181
7.3.2.2 General Procedure for the Catalytic Asymmetric Epoxidation of 2-
Cyclopentenones...................................................................................................................181
7.3.3 Synthesis of Antibacterial Agent (2S, 3S)-2-nor-Epoxy-Methylenomycin B.............187
7.3.4 Determination of the Absolute Configuration of 129p................................................188
7.4 Catalytic Asymmetric a-Alkylation of a-Branched Aldehydes..........................189
7.4.1 Preparation of the Starting Materials...........................................................................189
7.4.1.1 Preparation of a-Branched Aldehydes...................................................................189
7.4.1.2 Preparation of Electrophiles....................................................................................189
7.4.1.3 Preparation of Catalyst 158.....................................................................................191
7.4.2 General a-Alkylation Procedures..................................................................................193
7.4.2.1 General Procedure for Racemates Preparation....................................................193
7.4.2.2 General Procedure for the Catalytic Asymmetric a-Alkylation of Aldehydes ...193
8. BIBLIOGRAPHY...................................................................................................198
9. APPENDIX..............................................................................................................205
9.1 Structure Index.......................................................................................................205
9.2Erklarung.................................................................................................................211
9.3 Lebenslauf................................................................................................................212
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| spelling | Lee, Anna 1978- Verfasser (DE-588)1027859534 aut Asymmetric aminocatalysis Knoevenagel condensation, epoxidation of 2-cyclopentenones and alpha-alkylation of alpha-branched aldehydes vorgelegt von Anna Lee 2012 IX, 212 S. graph. Darst. txt rdacontent n rdamedia nc rdacarrier Köln, Univ., Diss., 2012 (DE-588)4113937-9 Hochschulschrift gnd-content HBZ Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=025432344&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Lee, Anna 1978- Asymmetric aminocatalysis Knoevenagel condensation, epoxidation of 2-cyclopentenones and alpha-alkylation of alpha-branched aldehydes |
| subject_GND | (DE-588)4113937-9 |
| title | Asymmetric aminocatalysis Knoevenagel condensation, epoxidation of 2-cyclopentenones and alpha-alkylation of alpha-branched aldehydes |
| title_auth | Asymmetric aminocatalysis Knoevenagel condensation, epoxidation of 2-cyclopentenones and alpha-alkylation of alpha-branched aldehydes |
| title_exact_search | Asymmetric aminocatalysis Knoevenagel condensation, epoxidation of 2-cyclopentenones and alpha-alkylation of alpha-branched aldehydes |
| title_full | Asymmetric aminocatalysis Knoevenagel condensation, epoxidation of 2-cyclopentenones and alpha-alkylation of alpha-branched aldehydes vorgelegt von Anna Lee |
| title_fullStr | Asymmetric aminocatalysis Knoevenagel condensation, epoxidation of 2-cyclopentenones and alpha-alkylation of alpha-branched aldehydes vorgelegt von Anna Lee |
| title_full_unstemmed | Asymmetric aminocatalysis Knoevenagel condensation, epoxidation of 2-cyclopentenones and alpha-alkylation of alpha-branched aldehydes vorgelegt von Anna Lee |
| title_short | Asymmetric aminocatalysis |
| title_sort | asymmetric aminocatalysis knoevenagel condensation epoxidation of 2 cyclopentenones and alpha alkylation of alpha branched aldehydes |
| title_sub | Knoevenagel condensation, epoxidation of 2-cyclopentenones and alpha-alkylation of alpha-branched aldehydes |
| topic_facet | Hochschulschrift |
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