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研究生: 蔡明山
Ming-Shan Tsai
論文名稱: 1.掌性雙烯三羰鐵錯合物的合成及鎳催化雙烯醛衍生物分子內環化反應 2.炔類化合物之半氫化還原反應
指導教授: 葉名倉
Yeh, Ming-Chang
學位類別: 博士
Doctor
系所名稱: 化學系
Department of Chemistry
論文出版年: 2002
畢業學年度: 90
語文別: 中文
論文頁數: 323
中文關鍵詞: 雙烯三羰鐵錯合物分子內環化半氫化還原
英文關鍵詞: diene tricarbonyl iron complexes, Nickel, intramolecular cyclization, semihydrogenation
論文種類: 學術論文
相關次數: 點閱:176下載:0
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  • 以(1S)-(+)-樟腦磺酮酸為掌性光學輔助基的環狀共軛雙烯分子與九羰基二鐵進行錯合反應,只得到一組非鏡像異構物之雙烯三羰鐵錯合物。若改以(1R)-(-)-樟腦磺酮酸為掌性光學輔助基時,則得到相對的鏡像異構物;具光學活性的環狀雙烯三羰鐵錯合物之立體化學由X-射線繞射儀解析得知。
    以催化量的Ni(cod)2、三苯化磷試劑及五當量的三乙基矽烷,能有效地使環狀1,3-共軛雙烯醛衍生物進行分子內環化反應,得到駢合(fused)及螺旋(spiro)雙環化合物。
    帶有-烷氧基的-不飽和炔酯及炔酮化合物,順利地以三苯化磷及水進行半氫化還原反應。帶有-烷氧基的-不飽和炔酯化合物還原為含順式及反式-不飽和烯酯化合物;而帶有-烷氧基的-不飽和炔酮化合物則只還原得到反式-不飽和烯酮化合物。

    Complexation of cyclic conjugated dienes, carrying a (1S)-(+)-ketopinoxy as the chiral auxiliary, with nonacarbonyldiiron proceeds in a completely diastereoselective fashion to afford diene–iron complexes in moderate yields.When (1R)-(–)-ketopinoxy was used as the chiral auxiliary, the opposite enantioisomeric complexes are isolated as a single diastereomer in comparable yield and specific rotation in each case. The stereochemistry of chiral cyclic conjugated diene–iron complexes is determined by single-crystal X-ray methods.
    Intramolecular cyclization of cyclic 1,3-dienes bearing an aldehyde group can be performed using Ni(cod)2 and triphenylphosphine as catalysts and excess of triethyl- silane. The above intramolecular cyclization allows the formation of fused- and spiro- bicyclic compounds.
    Semihydrogenation of -unsaturated ynoates and -ynones bearing a -alkoxy group can be performed using triphenylphosphine and water. -Unsaturated ynoates were reduced to a mixture of cis and trans -unsaturated enoates, whereas ynones
    were reduced to trans -unsaturated enones as the only products.

    目 錄 目錄 I-III 中文摘要 IV 英文摘要 V 第一章 緒論 1 第二章 以樟腦酮菘酸為光學輔助劑合成完全非鏡像立體選擇性之 掌性雙烯三羰鐵錯合物 II-1 前言 12 II-2 結果與討論 II-2-1 製備C-2位置帶光學輔助基之閉環雙烯化合物 33 II-2-2 製備C-1位置帶光學輔助基之閉環雙烯化合物 35 II-2-3 非鏡像異構物選擇性反應 37 II-3 結論 43 第三章 過渡金屬鎳催化雙烯醛衍生物分子內環化反應 III-1 前言 44 III-2 結果與討論 III-2-1 製備閉環1,3-共軛雙烯醛衍生物III-78a-c 57 III-2-2 製備閉環1,3-共軛雙烯醛衍生物III-88a-c 58 III-2-3 過渡金屬鎳催化閉環1,3-共軛雙烯醛衍生物III-78a-c 之分子內環化反應 59 III-2-4 過渡金屬鎳催化閉環1,3-共軛雙烯醛衍生物III-88a-c 之分子內環化反應 64 III-3 結論 70 第四章 三苯化磷催化炔類半氫化還原反應 IV-1 前言 71 IV-2 結果與討論 IV-2-1 製備帶有g-烷氧基的a,b-不飽和炔酯和炔酮化合物 80 IV-2-2 缺電子性炔丙醚化合物藉由三苯化磷還原為烯丙醚化合物81 IV-3 結論 84 第五章 實驗部分 V-1 分析儀器及基本實驗操作 85 V-2 實驗部分及光譜數據 V-2-1 一般實驗程序 87 V-2-2 樟腦酮菘酸的製備 92 V-2-3 合成具有光學活性的雙烯分子 93 V-2-4 具有光學活性的雙烯分子與Fe2(CO)9的錯合反應 97 V-2-5 共軛雙烯酯三羰鐵錯合物III-76a-c的製備 102 V-2-6 共軛雙烯酯三羰鐵錯合物III-85a-c的製備 102 V-2-7 共軛雙烯酯三羰鐵錯合物的去錯合反應 103 V-2-8 共軛雙烯酯化合物的保護基形成反應 108 V-2-9 共軛雙烯醛化合物的製備 110 V-2-10 過渡金屬鎳催化共軛雙烯醛衍生物的分子內環化反應 115 V-2-11 帶有g-烷氧基的a,b-不飽和炔酯和炔酮化合物的製備 121 V-2-12 帶有g-烷氧基的a,b-不飽和炔酯和炔酮化合物的半 氫化還原反應 126 V-2-13 半氫化還原反應的氘化實驗 135 第六章 參考文獻 137 附錄 141

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