Collective Total Syntheses of Taiwaniaquinoids

목차 (Table of Contents)

• Table of Contents i
• List of Table iii
• List of Figures iv
• List of Schemes v
• Abbreviations vii
• Abstract 1
• Ⅰ. Introduction 2
• 1. General aspects of the indane motifs 2
• 2. Taiwaniaquinoid family of natural products 3
• 2.1. Structure and biological activities 3
• 2.2. Biogenetic hypotheses of taiwaniaquinoids 4
• 3. Previous synthetic strategies for taiwaniaquinoids 5
• 3.1. B-ring contraction approaches 5
• 3.2. A to ABC approaches 6
• 3.3. Stepwise: C to BC to ABC approaches 7
• 3.4. AC to ABC approaches 7
• 3.4.1. Palladium-catalyzed C9-C10 bond formation 7
• 3.4.2. Lewis acid-catalyzed C9-C10 bond formation 8
• 3.4.3. Lewis acid-promoted cascade reaction to construct the [6,5,6] tricyclic core 9
• 3.5. A- and C- rings to ABC approaches 9
• 4. Challenges and our approach idea in the total synthesis of taiwaniaquinoids 10
• II. Results and Discussion 11
• 1. Summary of failed approaches 11
• 1.1. First generation route 11
• 1.1.1. Retrosynthetic analysis 11
• 1.1.2. Designing an advanced indanone intermediate 94 12
• 1.1.2.1. Model study 12
• 1.1.2.2. Preparation of known aldehyde compound 13
• 1.1.2.3. Synthesis of advanced intermediate indanone 94 14
• 1.1.2.4. The formal syntheses of dichroanal B, taiwaniaquinone D and taiwaniaquinols B, D 15
• 1.2. Second generation route 18
• 1.2.1. Retrosynthetic analysis 18
• 1.2.2. The formal synthesis of dichroanal B, taiwaniaquinone D and taiwaniaquinols B, D 19
• 1.2.3. The formal synthesis of taiwaniaquinol F 21
• 1.3. Third generation route 22
• 1.3.1. Retrosynthetic analysis 22
• 1.3.2. The formal synthesis of dichroanal B, taiwaniaquinone D and taiwaniaquinols B, D 22
• 2. Endgame 24
• 2.1. Retrosynthetic analysis 24
• 2.2. Divergent total synthesis of taiwaniaquinoids 25
• 2.2.1. The formal synthesis of taiwaniaquinol F 25
• 2.2.2. Completion of the total synthesis of taiwaniaquinone G 27
• 2.2.3. Completion of the total synthesis of taiwaniaquinol E 29
• 2.2.4. Completion of the formal synthesis of dichroanone and taiwaniaquinone H 30
• 2.2.5. The formal synthesis of dichroanal B, taiwaniaquinone D and taiwaniaquinols B, D 32
• III. Conclusion 34
• 1. Summary of work 34
• Ⅳ. Experimental Section 36
• 1. General Information 36
• 2. Synthesis and characterization of compounds 37
• Ⅴ. References 69
• Ⅵ. Appendix 73