有機過渡金屬鐵、鉻羰基錯合物的合成及其在有機合成上的應用

The synthesis and application of transition metal iron and chromium carbonyl complexes

黃彬峰(Huang Ping Feng)

指導教授 ： 葉名倉

國立臺灣師範大學/理學院/化學系/碩士(1999年)

摘要

1.(η7-環庚三烯基)三羰鉻陽離子錯鹽，與有機鋅銅試劑反應，生成7-exo-取代的（η6-環庚三烯）三羰鉻陽離子錯合物，但當（η6-環庚三烯）三羰鉻錯合物之環庚三烯有取代基時（methyl），即非常不穩定、易分解。
2.(η5-環己雙烯)三羰鐵陽離子錯鹽，與有機鋅銅試劑反應，生成5-官能化烷鏈之（η4-環己雙烯）三羰鐵錯合物，以NOBF4進行配位基置換，若雙烯上支鏈為含胺基烷鏈時，一方面因配位基NO使鐵錯合物不穩定，另一方面胺基與酸（COOH）不同之性質，致使含胺基烷鏈之鐵錯合物無法進行分子內環化反應得環化產物。
3.以樟腦酮菘酸為光學輔助基的環己雙烯衍生物與鐵錯合時，由於樟腦酮菘酸之立體效應與其上的酮基之導引作用，使鐵由特定方位進入而與雙烯錯合，得到1 個非鏡像異構物，將此三羰鐵錯合物以三苯碳陽離子移除氫陰離子，形成陽離子錯鹽，與鋅銅試劑反應，在-78℃下，可得官能化烷基取代之三羰鐵錯合物，再經水解，去錯合，可得optical pure的環己烯酮衍生物。

關鍵字

鐵鉻羰基錯合物

並列摘要

1. Reaction of (η7- tropylium) tricarbonylchromium tetrafloroborate with functionalized zinc-copper reagent gives 7-exo-substituted adduct of (η6- cycloheptatriene) tricarbonylchromium complex . Hydride abstraction of (η6- cycloheptatriene) tricarbonylchromium complex , bearing methyl group in cycloheptatriene , using Ph3CBF4 led to cation of (η7- methyl tropylium) tricarbonylchromium tetrafloroborate salt , and unfortunately it was very un- stable , easy to oxidize to decompose by oxygen of air .
2. Addition of specially functionalized zinc-copper reagent to (η5- cyclohexa- dienyl) tricarbonyliron cation salt afforded (η4- cyclohexadiene) iron complex with functionalized side chain of amino alkyl group at C-5 position. Treatment of the adduct with NOBF4，followed by Et3N at 0℃ failed to get intramolecular cyclization products. Because of ligand transformation by NO+ that produced more unstable iron cation, and the feature of amino group different from carboxylic group, it is failed to proceed intramolecular cyclization.
3. The complexation reaction of the 1,3-cyclohexadiene derivatives bearing the ketopinic acid derivatives as chiral auxiliary with Fe2(CO)9 led only one diastereomer because of the direct effect of keto group of chiral auxiliary and stereo effect of bucky group of chiral auxiliary occupied special orientation. Removing hydride of (η4-cyclohexadiene)tricarbonyliron complex bearing the ketopinic acid derivatives as chiral auxiliary by trityl cation led (η5- cyclohexadienyl)tricarbonyliron cation salts. Reaction of this iron cation salts with functionalized zinc-copper reagent produced corresponding substituted (η4- cyclohexadiene)tricarbonyliron complex, and got the optical pure cyclo -hexenone derivatives after hydrolysis and decomplexation.

並列關鍵字

iron and chromium carbonyl complex

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