Studies toward the Total Synthesis of Solanoeclepin A on the Basis of New Cyclobutane Ring Formation

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研究生：	曹國緯 Tsao, Kuo-Wei
論文名稱：	Studies toward the Total Synthesis of Solanoeclepin A on the Basis of New Cyclobutane Ring Formation
指導教授：	磯部稔 Minoru Isobe
口試委員:	廖俊臣汪炳鈞林俊成陳清玉
學位類別：	博士 Doctor
系所名稱：	理學院 - 化學系 Department of Chemistry
論文出版年：	2012
畢業學年度：	101
語文別：	英文
論文頁數：	230
中文關鍵詞：	環丁烷化合物、三圓環[5.2.1.01,6] 癸烯骨架、四級不對稱碳、[2,3]-Wittig重排反應
外文關鍵詞：	chiral cyclobutane, epoxy vinylsulfone, tricyclo[5.2.1.01,6]decene skeleton, acetylene-dicobalthexacarbonyl, [2,3]-Wittig rearrangement
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本論文之研究目的著重於開發新穎環化反應，以建構具有光學活性的四員環化合物，進而應用於天然物solanoeclepin A的合成。其中我們以(D)-和(L)-阿拉伯醣衍生物為起始物，經由數步的合成反應製備前驅物100及其鏡像異構物ent-100。之後利用heteroatom-directed conjugate addition方法誘導親核劑分別與環氧化合物100及其鏡像異構物ent-100進行加成反應與陰離子環化反應，可合成獲得環丁烷化合物115以及鏡像異構物ent-115。
另一方面，我們也利用[2,3]-Wittig重排反應引進C4橋頭碳上的反式炔丙醇107，其炔基與鈷金屬進行錯合反應以製備前驅物150。隨之經由Hosomi-Sakurai type的合成策略與鈷羰基錯合物150進行陽離子環化反應，可成功地建構solanieclepin A的三圓環[5.2.1.01,6] 癸烯骨架(CD環)，其包含四、五、六員環和三個四級不對稱碳原子。

中文摘要    i
Abstract    ...ii
Acknowledgment    ...iii
Abbreviations    ...iv
Contents    ...vi
Figure Index    ...x
Table Index    ...xi
Chapter I. Introduction    ....1
I-1. Introduction of Solanoeclepin A    ....1
I-1-1. Hatch-Stimulating Substance for Potato Cyst Nematodes    .....1
I-1-2. Synthetic Review of Solanoeclepin A    .....2
I-2. Introduction of Chiral Cyclobutane    .....6
I-2-1. Photochemical [2+2] Cycloaddition    .....7
I-2-2. Organometal-mediated Ring Contraction    .....8
I-2-3. Base-induced Intramolecular Cyclization of Epoxy Moiety    .....9
I-3. Heteroatom-Directed Conjugate Addition    .....11
I-3-1. Heteroactom-Directed Conjugate Addition toward the Synthesis of Natural Products    .....12
I-3-2. Acetylene-dicobalthexacarbonyl Carbocation ....13
I-4. Introduction of [2,3]-Wittig Rearrangement    .....14
I-4-1. Overview of [2,3]-Wittig Rearrangement    .....15
I-4-2. Stereochemical Control of [2,3]-Wittig Rearrangement    .....15
I-4-3. 1, 3- Chirality Transformation of [2,3]-Wittig Rearrangement    .....16
I-5. Research Motif and Proposal    .....19
I-5-1. Research Proposal- I of Chiral Cyclobutane .....19
I-5-2. Research Proposal- II of Tricyclo[5.2.1.01,6]decene System    .....19
Chapter II. Results and Discussion    .....22
II-1. Synthesis of Chiral Cyclobutane by Heteroatom-Directed Conjugate Addition    .....22
II-1-1. Synthesis the Epoxy Vinylsulfone 100    .....22
II-1-2. -Heteroatom-Directed Conjugate Addition .....23
II-1-3. Synthesis the Enantiomeric Precursor from L-Arabinal    .....27
II-1-4. Construction of Cyclobutanes by Heteroatom-Directed Conjugate Addition    .....28
II-2. Synthesis of Tricyclo[5.2.1.01,6]decene System toward Solanoeclepin A    .....36
II-2-1. Application of Hosomi- Sakurai Type Reaction .....36
II-2-2. Application of [3,3]-Sigmatropic Rearrangement and [2,3]- Wittig Rearrangement    .....40
II-2-3. Synthesis of Tricyclo[5.2.1.01,6]decene by [2,3]-Wittig Rearrange- ment and Hosomi-Sakurai Type Reaction    .....47
II-2-4. Gold-mediated Cyclization of Propargylic Alcohol 107    .....56
II-3. Conclusion    .....58
Chapter III. Experimental and References    .....60
III-1. General    ......60
III-2. Experimental Procedure    .....62
III-2-1.Synthesis of compound 102    .....62
III-2-2. Synthesis of compound 111    .....62
III-2-3. Synthesis of compound 101    .....63
III-2-4. Synthesis of D-series epoxy vinyl sulfone 100    ....64
III-2-5. Synthesis of compound 112a    .....65
III-2-6. Synthesis of compound 112b    .....66
III-2-7. Synthesis of compound 112c    .....67
III-2-8. Synthesis of compound 112d    .....68
III-2-9. Synthesis of compound 114    .....70
III-2-10. Synthesis of compound ent-112a    .....71
III-2-11. Synthesis of compound ent-112b    .....72
III-2-12. Synthesis of compound ent-112c    .....73
III-2-13. Synthesis of compound ent-112d    .....74
III-2-14. Four-member ring 113 and 114 formation under condition B.    .....76
III-2-15. Four-member ring 115 formation under condition C.    .....79
III-2-16. Synthesis of enantiomer cyclobutane ent-115a.    82
III-2-17. Synthesis of compound 123    ....84
III-2-18. Synthesis of compound 130    ....85
III-2-19. Synthesis of compound 131    ....86
III-2-20. Synthesis of compound 135    ....87
III-2-21. Synthesis of compound 136a    ....88
III-2-22. Synthesis of compound 141a    ....89
III-2-23. Synthesis of compound 145    ....90
III-2-24. Synthesis of compound 146    ....91
III-2-25. Synthesis of compound 147    ....92
III-2-26. Synthesis of compound 148    ....93
III-2-27. Synthesis of compound 136c    ....94
III-2-28. Synthesis of compound 149    ....95
III-2-29. Synthesis of compound 108    ....96
III-2-30. Synthesis of compound 107    ....98
III-2-31. Synthesis of compound 150    ....99
III-2-32. Synthesis of cyclobutane 151    ....100
III-2-33. Synthesis of compound 152    ....101
III-3. References    .....104
Appendix (I). X-ray data and NMR spectra of compounds    .....109
Appendix (II). Publishcation    .....226


Figure Index
Figure 1. Potato cyst nematode and cysts on a potato root    .....2
Figure 2. Cyclobutane skeleton in nature products    ..6
Figure 3. tricyclo[5.2.1.01,6]decene skeleton 84.    ..14
Figure 4. NOESY experiment of 112a.    ...24
Figure 5. 1H- and 13C-NMR spectra of 113a and 114a.    ..30
Figure 6. HMBC experiment of cyclobutane 113a.    ..31
Figure 7. HMBC experiment of cyclobutene 114a.    ...31
Figure 8. ORTEP of the crystal structure of cyclobutane 114b.    ....32
Figure 9. NOESY experiment of cyclobutene 113a.    ....33
Figure 10. ORTEP of the crystal structure of cyclobutane 115a.    ....34
Figure 11. ORTEP of the crystal structure of cyclobutane ent-115a.    ....35
Figure 12. NOESYexperiment of 123.    ....39
Figure 13. HMBC experiment of 123.    ....39
Figure 14. NOESY experiment of [2,3]-Wittig rearrangement product 143.    ....45
Figure 15. HMBC experiment of [2,3]-Wittig rearrangement product 143.    ....45
Figure 16. HMBC experiment of elimination product 142b.    ..46
Figure 17. NOESY experiment of 147.    ....50
Figure 18. NOESY experiment of 148.    51
Figure 19. 1H- and 13C-NMR spectra of 147 and 148.    ..52
Figure 20. HMBC experiment of 152.    ..54
Figure 21. NOESY experiment of 152.    ...54
Figure 22. 1H-NMR spectra of 107a, 150, 151 and 152.    ..56
Figure 23. ORTEP of the crystal structure of tricyclo[5.2.2.01,6]undecene 161.    ...57

Table Index

Table 1. HADCA of D-series 100 with various nucleophiles.    ...25
Table 2. HADCA of L-series ent-100 with various nucleophiles.    ....28
Table 3. Characteristic 1H- and 13C-NMR spectra data of 113a and 114a.    ....30
Table 4. Hosomi-Sakurai type reaction with various nucleophiles.    ....38
Table 5. Characteristic 1H- and 13C-NMR spectra data of 147 and 148.    ....51 
Table 6. Characteristic 1H-NMR spectra data of 107a, 150, 151 and 152.    ....55



                                

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