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研究生: 廖經瑋
Liao, Jin-Wei
論文名稱: 帶官能基(η4-環庚-1,3-雙烯)三羰鐵錯合物之分子內環化反應
指導教授: 葉名倉
Yeh, Ming-Chang
學位類別: 碩士
Master
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: 3
中文關鍵詞: 鋅銅試劑二異丙基胺鋰三羰鐵錯合物二碘化Sm橋狀雙環橋狀三環
英文關鍵詞: Knochel reagent, LDA, Bridged bicyclo, Bridged tricyclo, SmI2, Free radical
論文種類: 學術論文
相關次數: 點閱:409下載:0
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  • 摘 要 九羰二鐵與環庚三烯在無
    水乙醚溶液中加熱迴流,生成(η4-環庚三烯)三羰鐵錯合物 .(η4-環庚雙
    烯)三羰鐵錯合物經四氟硼除酸處理,可得(η5-環庚二烯)三羰鐵硼酸鹽
    錯合物.帶酯基及氰基的鋅銅機試劑與(η5-環庚雙烯)三羰鐵硼酸鹽錯合
    經物進行親核 取代反應,得到碳五長鏈帶官能基的(η4-環庚二烯)三羰鐵
    錯合物.在-78oC一大氣壓CO 氣體下,用二異丙基胺鋰(LDA)進行分子內環
    化反應時,可得到橋狀雙環[4.2.1]壬烷含醛 衍生物,改變終止反應的親電
    子試劑,如碘化甲烷,溴化甲苯,可得到橋狀三環[5.2.1.04,8] 葵烷衍生
    物,在-78oC下,用二異丙基胺鋰(LDA)進行分子內環化反應兩小時後,在一
    大氣壓 O2氣體室溫下繼續反應一小時.當以三氟醋酸終止反應時,可得橋
    狀雙環[4.2.1]含酸衍生 物. 帶酮基之環庚二烯三羰鐵錯合物與二碘化
    杉,進行分子內自由基環化反應,生成單一非鏡 像異構物的并環雙環
    [5.3.0]與[5.4.0]雙烯化合物.

    Part 1 Cycloheptatriene irontricarbonyl complexes was
    prepared in 58% yield by treatment of iron ninecarbonyl and
    cycloheptatriene in dry ether under nitrogen. Reaction of
    cycloheptatriene iron tricarbonyl complex with aqueous
    tetrafluoloborate cation salt (85%). The nucleophilic addition
    reaction of a variety of zinc-copper reagent with
    tricarbonyliron cation generated iron complexes with an ester
    and cyano derivative at C-5 position. Intramolecular cyclization
    of the complex using lithium diisopropylamide(LDA, 1.2 equiv.)
    in THF and hexametheylphosphoramide (HMPA, THF/HMPA = 3:1) at
    -78oC for 2hr under an atmosphere of carbon monoxide (14 psi)
    followed by quenching the reaction mixture with TFA (10 equiv)
    produced the bicyclo[4.2.1]nonanecar- oxylic acid derivatives.
    Interestingly, the reaction underwent different pathways by
    quenching the reaction mixture with carbon electrophiles such as
    iodomethane or benyl bromide gave tricyclo[5.2.1.04,8
    ]decanecarboxylic acid deritaves. Intramolecular cyclization of
    complexes using lithium diisopropyl amide at -78oC for 2hr
    followed by quenching the reaction intermediate with molecular
    oxygen produced bicyclo[4.2.1]nonanecarboxylic acid derivatives.
    Part 2 Intramolecular radical cyclization of iron (η4-
    cyclohepta-1,3-diene) complexes bearing a keto functionality
    proceeded nicely in presence samarium iodide (SmI2) to give
    fused bicyclo[5.4.0] and [5.3.0] derivatives with extreme
    diastereoselectivity.
    Part 1 Cycloheptatriene irontricarbonyl complexes was

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