有機過渡金屬鐵羰基錯合物在有機合成上的應用

Applications of transition Iron-tricarbonyl complexes in organic syntheses

薛朋雨(Peng-Yu Hsueh)

指導教授 ： 葉名倉

國立臺灣師範大學/理學院/化學系/碩士(2000年)

摘要

本論文共分成三部份：
以三羰基鐵活化後的共軛雙烯，在25℃下，碳的親核性試劑加成到（h4-1,3雙烯）三羰鐵錯合物後，所得的中間體與Davis reagent反應，在閉環系統中以得到C-5位置親核取代的雙烯鐵錯合物為主；而開環系統則以得到終端位置親核取代的雙烯鐵錯合物為主。以有機矽陰離子為親核性試劑與雙烯三羰鐵錯合物進行加成反應，再以Davis reagent終止反應所得到的產物，亦保持原本雙烯三羰鐵的構造；然而以三氟醋酸或溴為親電子性試劑所得到的產物則可得到一系列的有機矽化物。
利用C-2位置帶酯基的（h4-雙烯）三羰鐵錯合物，在25℃下與二異丙基胺鋰（LDA），進行分子內親核性反應，其反應機構為親核性試劑攻擊（h4-雙烯）三羰鐵錯合物的C-2位置上，造成碳-氧鍵斷裂離去，得到γ-內酯的產物；而C-2位置帶氰基的（h4-雙烯）三羰鐵錯合物，在-78℃或25℃下，進行相同的親核性反應，得到一組非鏡像異構物。
利用C-2位置帶(1S)-(+)-樟腦磺酮酸為光學輔助劑的開環雙烯化合物，與九羰基二鐵進行錯合反應，由於樟腦磺酮酸的立體效應及酮基的引導作用，使三羰鐵由特定方向與雙烯錯合，可得到非鏡像異構物超越值（de值）＞99%的異構物；改以(1R)-(-)-樟腦磺酮酸為光學輔助劑，可得到相對應的鏡像產物，其de值亦大於99%的非鏡像異構物，其立體結構可由 X-ray 繞射結構解析得知。

關鍵字

有機過渡金屬 ； 有機合成

並列摘要

The addition of carbon nucleophiles at 25℃ to (h4-1,3-cyclohexadiene)Fe(CO)3 complex followed by hydride abstraction with Davis reagent produces C-5 substituted (h4-1,3-cyclohexadiene)Fe(CO)3 complexes as the major products. With acyclic diene-
iron complexes, the addition gave predominantly terminal nucleophilic-substituted (h4-
1,3-diene)Fe(CO)3 complexes. The silicon anion (LiSiMe2Ph) is capable of addition and afford silicon-substituted iron-complex. The reaction path is similar to that of carbon nucleophiles. Quenching the reactive intermediate with trifluoroacetic acid or bromines generated organosilicon compounds.
Intramolecular addition of ester enolate to iron-complex with an ether linkage at the C-2 position of the diene generates g-lactones as the major product. The reaction involved first addition/elimination followed by intramolecular transesterfication to give the g-lactones.
Complexation of acyclic dienes, carrying a (1S)-(+)-ketopinoxy as the chiral auxiliary, with Fe2(CO)9 proceeds in a completely diastereoselective fashion to afford diene-iron complexes in moderate yields. When (1R)-(-)-ketopinoxy was used as the chiral auxiliary, the opposite enantioisomeric complexes are isolated as a single diastereomer in comparable yield and specific rotation. The stereochemistry of chiral acyclic diene-iron complexes is determined by single-crystal X-ray methods.

並列關鍵字

transition Iron-tricarbonyl complexes ； organic syntheses

參考文獻

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