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研究生： 倪永朋
Supaporn Niyomchon
論文名稱： Carbon-Carbon Bond Formation From Heteroconjugate Addition Reactions ofUnsaturated Sulfones---Studying Toward Cyclobutane Synthesis
指導教授： 磯部稔
Minoru Isobe
口試委員:
學位類別： 碩士
Master
系所名稱： 理學院 - 化學系
Department of Chemistry
論文出版年： 2010
畢業學年度： 98
語文別： 英文
論文頁數： 192
中文關鍵詞： 雜加成反應 、不飽和碸 、環丁烷
外文關鍵詞： Hetroconjugate addition, unsaturated sulfone, cyclobutane
相關次數： 點閱：14  下載：0 
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    • Heteroconjugate addition of carbon nucleophile to unsaturated sulfones is known to result in C-C bond formation. This concept was extended to utilize the carbanion intermediate for epoxide opening to end up with the formation of cyclobutane ring with stereochemical control.

    Study of the vinyl sulfone system indicates that the relative stereochemistry of epoxide (syn-/anti-) to the sulfonyl group is important for the cyclization step. In the limited case of compound 65a, the epoxide situated anti to the sulfone-stabilized carbanion intermediate, which led us to obtain the cyclobutane compound 64 in regio- and stereoselective manner.

    Not only the Brook rearrangement, in which the silly group migration from carbon to oxygen atom was obtained as the compound 59a, but also Payne rearrangement took place to give compound 59b and 59c. During the course of studies, the spiro-cyclobutene 63 was coincidentally achieved in case of compound 48b, in which the epoxide was situated syn to the sulfone-stabilized carbanion.

    In addition, the acetylene sulfone (alkynyl sulfone) system was also investigated. Some nucleophile provided the characteristic conjugate addition product, but some nucleophile afforded displacement product at the sulfonyl group to give alkynyl-Nu.

    Contents 中文摘要 i Abstract iii Acknowledgement iv Contents vi Figure index vii Table index viii Scheme index ix Abbreviation. x Chapter 1. Introduction 1.1. Cyclobutane moieties in natural products 1 1.2. Solanoeclepin A 2 1.3. Reviews on the synthesis of Solanoeclepin A 2 1.4. Heteroconjugate addition reaction of unsaturated-sulfones 6 1.4.1. Heteroconjugate addition reaction of α-silyl substituted vinyl sulfones 6 1.4.2. Heteroconjugate addition reaction of acetylene sulfones 8 Chapter 2. Carbon-Carbon bond formation from heteroconjugate addition of vinyl sulfone system for cyclobutane synthesis 2.1. Results and discussion 10 2.2. Conclusion 27 2.3. Experimental section and supporting data 29 Chapter 3. Carbon-Carbon bond formation from heteroconjugate addition of acetylene sulfone system for cyclobutane synthesis 3.1. Results and Discussion 45 3.2. Conclusion 51 3.3. Experimental section and supporting data 52 Supporting information I: Crystal data of compound 59c 65 Supporting information II: Crystal data of compound 63 89 Supporting information III: Crystal data of compound 65a 118 Supporting information IV: Crystal data of compound 64 126 Supporting information V: NMR spectra of synthesized compounds 145

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