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Synthesis of oxygen and nitrogen heterocycles via stabilized carbocations and
ring closing metathesis.
Doodeman, R.
Publication date
2002
Link to publication
Citation for published version (APA):
Doodeman, R. (2002). Synthesis of oxygen and nitrogen heterocycles via stabilized
carbocations and ring closing metathesis.
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CONTENTS S
CHAPTERR 1 INTRODUCTION
1.11 Carbocations Stabilized by Oxygen and Nitrogen 1 1.1.11 Oxycarbenium and Iminium Ion Chemistry 1
1.1.22 N-Acyliminium Ion Chemistry 2 1.1.33 Intermolecular N-Acyliminium Ion Reactions 3
1.1.44 Intramolecular Af-Acyliminium Ion Reactions 4
1.22 Olefin Metathesis 8 1.2.11 Introduction 8 1.2.22 Mechanism 8 1.2.33 Mo-based Catalysts 9 1.2.44 Ru-based Catalysts 10 1.33 General Aspects 12 1.3.11 (£)/(Z)-Ratio 12 1.3.22 Enyne Metathesis 12 1.44 Purpose and Outline of the Investigation 14
1.55 References 14 CHAPTERR 2 2-SUBSTITUTED-2H-CHROMENES 17 2.11 Introduction 17 2.22 Preparation of RCM Precursors 19 2.2.11 Mechanistic Aspects 20 2.33 Ring-Closing Metathesis 21
2.3.11 Synthesis of the Catalysts 21 2.3.22 Ring Closure to Chromenes 22 2.44 1-Benzopyrylium Ion Chemistry 23 2.55 Functionalization at the 4-Position 26
2.66 Conclusions 29 2.77 Acknowledgements 29 2.88 Experimental Section 30 2.99 References and Notes 43
CHAPTERR 3 4,5-DISUBSTITUTED TRANS-FUSED BICYCLIC LACTAMS
3.11 Introduction 45 3.22 Literature Strategies 46 3.33 Preparation of Starting Isopropoxylactam 49
3.44 Synthesis of N-Acyliminium Ion Precursors 51
3.4.11 Michael Addition 51 3.4.22 Cuprate Addition 54 3.55 N-Acyliminium Ion Reaction 55
3.5.11 Ene-ene Disubstituted Lactams 55 3.5.22 Enyne Disubstituted Lactams 57
3.66 Ring-Closing Metathesis 58 3.6.11 Ene-ene Metathesis 58 3.6.22 Enyne Metathesis 62 3.77 Discussion, Conclusions and Outlook 64
3.88 Acknowledgements 64 3.99 Experimental Section 65
3.100 References 83
CHAPTERR 4 BRIDGED AZABICYCLIC SYSTEMS
4.11 Introduction 87 4.22 Literature Strategies 88 4.33 Imides as Substrates 92 4.44 Isopropoxylactams as Substrates 94
4.55 Nitrogen Adjacent to a Bridgehead Position 96
4.66 Azabicyclo[4.x.l]alkenes 99 4.6.11 Precursor Synthesis 99 4.6.22 N-Acyliminium Ion Chemistry 100
4.6.33 RCM to Azabicyclo[4.2.1]non-3-enes 102 4.6.44 RCM to AzabicycIo[4.3.1]dec-3-enes 104 4.77 Conclusions 105 4.88 Acknowledgements 105 4.99 Experimental Section 105 4.100 References 122 SUMMARYY 125 SAMENVATTING G 129 9
