臺灣博碩士論文加值系統

本論文以C-6 位置接有不同長度碳鏈取代基之4-苯硫基二氫吡啶酮(3)與methyl acrylate 進行交叉歧化反應，可得到化合物51，再經Bu3SnH/AIBN 切除氮上Ts 基得到化合物52，在鹼性條件下進行分子內共軛加成反應，可得到雙環二氫吡啶酮衍生物53，並探討環化反應的立體選擇性。
在低溫下利用LiAlH4 將化合物53a (cis/trans 1:1)的酯基還原，可得到醇基化合物cis-63 與trans-63。化合物cis-63 再進行溴化反應，緊接著可進行去溴化反應，得到化合物cis-65，將化合物cis-65 以Raney nickel 切除碳硫鍵並還原C=C 雙鍵可得到化合物cis-66，再與Grignard 試劑進行1,2-加成反應，利用醋酸脫水，再與hydride 反應，可順利合成生物鹼indolizidine (±)-167E。我們利用相同策略先將化合物53b 的酯基還原，可得到醇基化合物68。化合物68 進行溴化反應，再與甲基酮試劑進行取代反應，得到化合物71。化合物71 若先與Grignard 試劑進行1,2-加成反應，利用醋酸脫水，再與hydride 反應，則得到化合物75，最後以Raney nickel切除碳硫鍵並還原C=C 雙鍵，得到文獻報導生物鹼quinolizidine 195C結構之化合物78，但二者光譜並不盡相同，因此生物鹼quinolizidine195C 的確實結構仍然未知。

This thesis used the cross metathesis of C ‐ 6 substituted 4-phenylthio-5,6-dihydro-2-pyridones (3) with methyl acrylate to synthesize compounds 51. Further treatment with Bu3SnH/AIBN led to the detosylation compounds 52. The bicyclic piperidines 53 could be obtained by intramolecular aza-Michael reaction of compounds 52 under
basic conditions. We also studied the diastereoselectivity of the cyclization reaction.
Reduction of the ester group of compound 53a (cis/trans 1:1) by treatment with LiAlH4 at low temperature afforded compounds cis-63 and trans-63. Bromination of compound cis-63, followed by debromination reaction gave compound cis-65. Reaction of compound cis-65 with Raney nickel both cleaved the C－S bond and reduced the C=C bond to give compound cis-66. Further treatment of compound cis-66 with methylmagnesium bromide, followed by acidification with acetic acid, and reduction with sodium borohydride accomplished the synthesis of (±)-indolizidine 167E.
We also applied this strategy to synthesize compound 71 from ester 53b through alcohol 68. Compound 71 was subsequently converted to compound 75, which was treated with Raney nickel to afford compound 78, the proposed structure for quinolizidine 195C. But the spectral data of compound 78 differed significantly from those reported in the literature for quinolizidine 195C. Thus the true structure of quinolizidine 195C remains uncertain.

中文摘要....................i
英文摘要....................iii
簡稱對照表...................v
表(Table)目錄...............vi
圖(F igu re)目錄............vii
流程圖(Scheme)目錄...........viii
緒論........................1
研究目標.....................12
實驗結果與討論................13
結論.........................61
使用之儀器、藥品和溶劑..........63
實驗步驟及光譜數據..............66
參考文獻......................104
附錄一(光譜)...................109
附錄二(2-D 光譜)...............252
附錄三(X-ray).................313

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