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研究生: 王正隆
Wang Jeng-Long
論文名稱: 帶官能基過渡金屬鐵、鈷羰基錯合物之分子內環化反應
Intramolecular cyclization of iron,cobalt complexes
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: 83
語文別: 中文
論文頁數: 326
中文關鍵詞: 鋅銅試劑,分子內環化反應,非鏡像立體超越值,
英文關鍵詞: zinc-copper reagent,intramolecular cyclization,
論文種類: 學術論文
相關次數: 點閱:274下載:3
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  • 本論文主要在探討有機過渡金屬鐵、鈷羰基錯合物與帶官能基鋅銅試劑及胺基酸
    衍生物的加成反應。再利用分子內環化反應,合成連結雙環化和物或含氮的雜環化合物。

    帶官能基的鋅銅試劑 RCu(CN)ZnI 與(η4-戊二烯醛)三羰鐵錯合物在路易士酸的催化下
    進行加成反應,產生一對非鏡像立體異構物,其非鏡像立體超越值最高可達86%

    帶官能基的鋅銅試劑 RCu(CN)ZnI 與(η4-2-甲醯基-丁二烯)三羰鐵錯合物,在路易士酸(
    BF3.OEt2)的催化下進行加成反應,產生一對非鏡像立體異構物,其非鏡像立體超越值最高
    可達90%。將側鏈為三個碳含氰基取代之雙烯醇錯合物與LDA作用,在-78℃下進行分子內環
    化反應,產生(σ,η3-烯丙基)三羰鐵錯合物。在相同條件下(-78℃),側鏈為三個碳含氰
    基取代之雙烯醇錯合物,經分子內環化反應後得到四羰基雙環[4.3.0]鐵壬酮。當反應溫度
    控制在25℃時,分子內環化反應的產物是三亞甲基甲烷形式的鐵錯合物。此三種產物的結
    構,均有X-ray單晶繞射圖加以證明。

    α-及 β-胺基酸衍生物可以和炔丙基六羰雙鈷陽離子進行加成反應,產生炔丙基接氮衍生
    物的六羰雙鈷錯合物。以硝酸鐵(III)將其氧化得到炔丙基胺化合物,以LDA進行分子內環
    化反應得到dihydropyrrole,再以DDQ氧化成pyrrole衍生物。Dihydrofuran及環戊烯也能
    以相同的方式合成。

    The main purpose of this thesis is to investigate the addition of
    functionalized zinc-copper reagents and amino acid derivatives to diene-
    tricarbonyliron and alkyne-hexacarbonyldicobalt complexes respectively.
    Intramolecular cyclization of the resulting adducts was further studied.

    Addition of functionalized zinc-copper reagents to (diene-aldehyde)Fe(CO)3
    complexes in the presence of Lewis acid proceeds in a highly
    diastereoselective fashion to afford dienol complexes. The best
    diastereomeric excess of adducts is up to 86%.

    The addition of a variety of highly functionalized zinc-copper reagents
    RCu(CN)ZnI to (η4-2-formylbuta-1,3-diene)Fe(CO)3 complex in the presence
    of an excess of boron trifluoride etherate proceeds in a highly
    diastereoselective fashion to afford dienol complexes in good yields.
    Intermolecular cyclolization of a cyano-substituted dienol complex
    containing a three-carbon side chain using LDA produces (σ,η3-allyl)
    tricarbonyliron complexes,whereas treatments of the cyano-substituted
    dienol complex containing a three-carbon side chain with LDA furnishes
    fused tetracarbonyl bicyclo[4.3.0]ferranonanones at -78℃ and
    complexes of trimethylenemethane type at 25℃.

    The addition of α-and β-amino acid derivatives to the cobalt stablized
    propargylic cations give dicobalthexacarbonyl complexes with amino acid
    derivatives at the propargyl position. Oxidation of the resulting complexes
    with Fe(III) or Ce(IV) produces propargyl amines. Intramolecular
    cyclolization of propargyl amines with LDA affords dihydropyrrole
    derivatives as the major products. Dihydrofuran and cyclopentene derivatives
    can also be synthesized by using the same approach.
    The main purpose of this thesis is to investigate the addition of

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