臺灣博碩士論文加值系統

本實驗室利用具有C2對稱的L-(+)-Tartaric acid為起始物作為(-)-Pericosine B全合成的開端。我們的合成策略運用L-酒石酸本身C2對稱，經由三步反應得到cyclohexenediol，接著加入乙醯氧基異丁醯氯(2-acetoxy isobutyryl chloride)，在鹼性條件下形成epoxide化合物，再以丙二腈(malononitrile)將epoxide開環、及過氧鄰苯二甲酸鎂鹽水解得到不飽和酯類。
<策略一>利用m-CPBA得到朝後環氧化合物，再進行羥基脫去形成雙鍵。之後希望以甲醇鈉進行1,2加成開環，再以戴斯－馬丁氧化劑 (Dess-Martin periodinane)形成不飽和酮，最後再以硼氫化鈉及七水化鈰(CeCl3•7H2O)合成出朝上的羥基，進而得到前趨物。最後便以三氟醋酸去除保護基，希望能於共12步的反應中得到最終產物(-)-Pericosine B。
<策略二>由不飽和酯類加入Trichloroisocyanuric acid 將烯類雙鍵轉化成chlorohydrin 69，再進行羥基脫去形成雙鍵，之後加入硝酸銀進行SN1反應得到methoxy化合物71，最後便以三氟醋酸(TFA)去除保護基，希望能於共10步的反應中得到最終產物(-)-Pericosine B。

Our lab has developed a rapid and efficient route to synthesize (-)-Pericosine B. We utilize L-tartaric acid which has C2-symmetric structure as starting material. Due to reason above, we can get cyclohexenediol through three steps. After that, subsequent of the cyclohexnediol with 2-acetoxyisobutyrylcholirde provide the desired acetoxychloride. Next, epoxide could be synthesized via acetoxychloride under the basic condition. Further, we used malononitrile for ring opening reaction. Once we get the cyano compound, it will soon follow with magnesium monoperoxyphthalate hexahydrate and cesium carbonate for hydrolysis to obtain ester.
< Strategy I > We took m-CPBA for oxidation reagent to get the epoxide then mesylation for next step. Then, we will try 1,2-ring opening reaction and reduction by sodium borohydride with cerium (III) chloride heptahydrate . Finally, we will remove protecting group by trifluoroacetic acid. we hope to complete the total synthesis of (-)-Pericosine B in 12 steps.
< Strategy II > We add Trichloroisocyanuric acid to get chlorohydrin 69 then add AgNO3 with MeOH to do SN1 reaction then get methoxy compound 71 , then we will remove protecting group by trifluoroacetic acid, to complete the total synthesis of (-)-Pericosine B in 10 steps.

摘要 i
Abstract ii
目錄 iii
圖目錄 iv
Equation 目錄 v
表目錄 vi
Scheme 目錄 vii
縮寫表(Abbreviations) viii
一、緒論 1
二、(-)-Pericosine B 之逆合成分析 8
三、結果與討論 9
四、結論 19
五、儀器與試劑 22
六、實驗步驟 24
七、參考文獻 39
八、光譜數據 42

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