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