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