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研究生: 莊麗紋
Chuang, Li-Wen
論文名稱: 以雙烯鐵羰基錯合物為媒介合成雙環,三環及雜環化合物
Construction of Fused Bicyclo and Tricyclo Skeletons via
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
畢業學年度: 84
語文別: 中文
論文頁數: 2
中文關鍵詞: 鋅銅試劑環化反應雙環化合物雜環化合物二異丙基胺鋰胺基酸衍生物
英文關鍵詞: zinc copper reagent, cyclization, Bicyclic compound, hetero compound, LDA, amino acid derivatives
論文種類: 學術論文
相關次數: 點閱:264下載:4
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  • 摘要 本論文主要在探討過渡金
    屬鐵錯合物與親核試劑的加成反應. 再利用加成後的產物進行分子內環化
    反應,合成聯結雙環,三環或雜環化合物. (η5-戊二烯)三羰鐵陽離子錯
    鹽與帶官基的鋅銅試劑進行加成反應,形成側鏈帶官基的雙烯三羰鐵錯合
    物,此錯合物以LDA在一大氣壓一氧化碳下,進行分子內環化反應,可得一系
    列高立體選擇性的雙環或三環化合物. 而當親核試劑改為胺基酸衍生物
    時,所得的錯合物進行同樣的分子內環化反應,產生三環含氮的雜環化合
    物. 高選擇性多官能化的五員環或六員環衍生物一直是複雜天然物的
    合成起始物. 以側鏈帶官能基的雙烯三羰鐵錯合物,在二異丙基胺基鋰(
    LDA)下進行分子內環化反應,接著通入一大氣壓的氧氣,氧化高丙烯鐵陰離
    子錯合物,可得到三取代高立體選擇性的五員環及六員環酸衍生物. 將
    側鏈帶酯基的雙烯三羰鐵錯合物,於鹼中水解,得帶酸基的雙烯三羰鐵錯合
    物後,用四氟硼酸亞硝醯置換鐵錯合物上的CO,然後進行分子內環化反應,
    產生一系列內酯化合物. 帶官能基雙烯三羰鐵錯合物,亦可在路易士酸
    的催化下,產生(σ,η3-烯丙基)三羰鐵錯 合物.

    Abstract Sequential
    additions of nucleophiles to (η5-dienyl)tricarbonyliron cation
    salts is the main purpose of this thesis. Intramolecular cycli-
    zation of the resulting adducts was futher studied. Addition
    of fuctionalized zinc copper reagents to (η5-pentadienyl)Fe(
    CO)3 cation salts afforded (η4-diene)iron complexes with
    functionalizedside chains at the terminal position of the diene
    ligands. Treatment of theadducts with LDA under an atmosphere of
    carbon monoxide furnished fused bicyclo[3.3.0]octane, -[4.3.0
    ]nonane and tricyclo[6.3.0.02,6]undecanederivatives. Using the
    same methodology, nitrogen-containing tricyclo-[6.3.0.02,6
    ]undecane, -[7.3.0.02,7]dodecane and -[6.3.1.02,6
    ]dodecanederivatives can be synthsized. The stereoselective
    preparation of highly functionalized five- and six-membered
    rings is an important synthetic goal since such ring
    skeletonsare present in numerous natural products of biological
    interest. Reactionof (η4-diene)Fe(CO)3 complexes bearing
    functionalized side chains with LDAat -78oC for 2h, followed by
    oxidation of the homoallyliron anion gave trisubstituted
    cyclopentane- and cyclohexanecarboxylic acid derivatives.
    Reaction of ester-functionalized diene complexes with KOH
    produced the corresponding acid complexes. Intramolecular
    cyclization of acid complexesusing NOBF4 followed by addition of
    Et3N gave lactone derivatives. Reaction of carboester
    functionalized (η4-diene)iron complexes with catalytic amount
    of Lewis acid afforded (σ,η3-allyl)tricarbonylironcomplexes.
    Abstract Sequential

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