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Studies towards the total synthesis of solanoeclepin A: synthesis of analogues
containing the tetracyclic left-hand substructure.
Benningshof, J.C.J.
Publication date
2001
Link to publication
Citation for published version (APA):
Benningshof, J. C. J. (2001). Studies towards the total synthesis of solanoeclepin A: synthesis
of analogues containing the tetracyclic left-hand substructure.
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Contents s
Chapterr 1 General Introduction
1.11 The Potato Cyst Nematode 1
1.22 Solanoeclepin A 3 1.33 Glycinoeclepin A 4 1.44 Hatching Activity Tests 5 1.55 Synthesis of Solanoeclepin A 5 1.66 Purpose and Outline of this Investigation 7
1.77 Acknowledgments 8 1.88 References and Notes 8
Chapterr 2 Synthesis of the Left-Hand Substructure of Solanoeclepin A
2.11 Introduction 11 2.22 Strategy 12
2.2.11 Intramolecular Furan Diels-Alder Reaction 12
2.2.22 Retrosynthesis 15 2.33 Results and Discussion 15
2.3.11 The Asymmetric Intramolecular Diels-Alder Reaction 15 2.3.22 Non-Reductive Removal of the JV-Substituent and further 17
Transformationn of the Lactam
2.3.33 Hydroboration and Completion of the Left-Hand Fragment 19
2.3.44 Introduction of the Vinyl Group 21
2.44 Concluding Remarks 22 2.55 Acknowledgments 23 2.66 Experimental Section 23 2.77 References and Notes 37
Chapterr 3 Attempted Seven-Membered Ring Formation via Carbonyl Coupling 3.1 1 3.2 2 3.3 3 3.4 4 3.5 5 3.6 6 3.7 7 Introduction n Strategy y
3.2.11 The Intramolecular Acyloin Condensation 3.2.22 McMurry Coupling
Resultss and Discussion
3.3.11 Chromium-Mediated Coupling Reaction 3.3.22 Formation of the Dialdehyde
3.3.33 Formation of a Triene Concludingg Remarks Acknowledgments s Experimentall Section Referencess and Notes
39 9 40 0 40 0 42 2 43 3 43 3 46 6 47 7 48 8 49 9 49 9 57 7
Chapterr 4 Seven-Membered Ring Formation via Ring-Closing Metathesis
4.1 1 4.2 2 4.3 3 4.4 4 4.5 5 4.6 6 4.7 7 Introduction n Strategy y 4.2.11 Ring-Closing Metathesis 4.2.22 Retrosynthesis Resultss and Discussion
4.3.11 Chromium-Mediated Coupling
4.3.22 Synthesis of the Ring-Closing Metathesis Precursor 4.3.33 Ring-Closing Metathesis
4.3.44 Introduction of the Oxygen Substituents
4.3.55 Completion of the Synthesis and Hatching Activity Tests Concludingg Remarks
Acknowledgments s Experimentall Section Referencess and Notes
59 9 60 0 61 1 64 4 64 4 64 4 66 6 68 8 69 9 72 2 75 5 76 6 76 6 85 5
Chapterr 5 Elaborate Model Compounds of Solanoeclepin A 5.1 1 5.2 2 5.3 3 5.4 4 5.5 5 5.6 6 5.7 7 Introduction n Strategy y 5.2.11 Enantioselective Cyclopropanation 5.2.22 Retrosynthesis
Resultss and Discussion
5.3.11 Synthesis of the Right-Hand Fragments
5.3.22 Chromium-Mediated Coupling and Synthesis of the Ring-Closingg Metathesis Precursors
5.3.33 Ring-Closing Metathesis and Oxidative Functionalization of the Seven-Memberedd Ring
5.3.44 Completion of the Synthesis 5.3.55 Hatching Activity Tests Concludingg Remarks
Acknowledgments s Experimentall Section Referencess and Notes
89 9 90 0 90 0 92 2 94 4 94 4 98 8 100 0 102 2 104 4 106 6 107 7 107 7 129 9 Summaryy 131 Samenvatting g 135 5
