姚清發Yao, Ching-Fa沈高賢Shen, Kao-Hsien2019-09-042009-1-12019-09-042006http://etds.lib.ntnu.edu.tw/cgi-bin/gs32/gsweb.cgi?o=dstdcdr&s=id=%22GN0891420081%22.&%22.id.&http://rportal.lib.ntnu.edu.tw:80/handle/20.500.12235/101007中 文 摘 要 第一部份 本研究之目的在觀察三丙烯基鋁試劑(triallylaluminum)，與α,β-不飽和硝基烯類化合物，在 0℃之條件下，進行丙烯基化(allylation)反應，而產生4,5-不飽和硝基烯類之探討。實驗結果顯示:三丙烯基鋁試劑與各種不同苯環取代基之β-硝基苯乙烯進行丙烯基化反應，可得高產率的4,5-不飽和硝基烯類。當三丙烯基鋁試劑與帶有烷基立體障礙較大之 α,β-不飽和硝基烯類進行反應時，加入三氯化鋁進行催化可使4,5-不飽和硝基烯類之產率明顯提升。本研究論文所採用三烯丙基鋁試劑是直接由鋁與丙烯溴(allyl bromide)反應而製得，並非經由葛理鈉試劑(Grignard reagent)和鹵化鋁之反應而間接製得。 第二部份 本研究論文是第一個使用以三丙烯基鋁試劑分別與羰基化合物(carbonyl compounds)或亞胺(imine)進行丙烯基化(allylation)反應之報導。至目前為止，除葛理鈉試劑(Grignard reagent)外，三丙烯基鋁試劑係不需任何金屬鹽類催化劑即可與醛亞胺(aldimine)、酮亞胺(ketimine)進行丙烯基化反應。由實驗結果顯示:三丙烯基鋁試劑是一個優良丙烯基化試劑，可與醛、酮進行丙烯基化反應，而得高產率homoallylic alcohol；同時它亦可與醛亞胺、酮亞胺進行丙烯基化反應而得高產率的homoallylic amine。三丙烯基鋁試劑特色之一是它亦可與剛性立體結構的金剛烷酮反應而產生甚佳之結果(98%產率)。此外，三丙烯基鋁試劑對ketoester具有良好的化學選擇性。本文特色之一是所採用的三丙烯基鋁試劑是直接由鋁與丙烯溴(allyl bromide)反應而產生，並非由間接葛理鈉試劑和其他鹵化鋁反應而製得。 第三部份 本研究論文是以三丙烯基鋁試劑(triallylaluminum)，對羧酸衍生物進行孿位的雙丙烯基化(gem-diallylation)反應。本文所採用三丙烯基鋁試劑是直接由鋁與丙烯溴(allyl bromide)反應而製得，並非由葛理鈉試劑(Grignard reagent) 反應而製得。三丙烯基鋁試劑具有化學選擇性及位置選擇性，可分別由三丙烯基鋁試劑與巴豆酸甲酯(methyl crotonate)或氯化肉桂醯基(cinnamoyl chloride)、肉桂酸甲酯(methyl cinnamate)等反應之結果而得到證明。Abstract Part one The reaction of aryl substituted α,β-unsaturated nitroalkenes with triallylaluminum in ether solution at 0 ℃ generated low to high yields of 4,5-unsaturated nitroalkenes after adding the nitronate to an ice cold solution of dilute hydrobromic acid. Triallylaluminum reacted with β-nitrostyrenes to give 4,5-unsaturated nitroalkenes in excellent yields. The yields of products were increased substantially when the alkyl substituted α,β-unsaturated nitroalkene and the highly hindered α,β-unsaturated nitroalkenes 1i and 1j were reacted with triallylaluminum in the presence of aluminum chloride. The most important advantage of using triallylaluminum 2 in this kind of reaction is that reagent 2 could be prepared from allyl bromide and pure elemental Al directly, but not from Grignard reagent and aluminum halide indirectly. Part two This is the first report of employing triallylaluminum asa reagent in the allylation of carbonyl compounds and imines. The allylation of ketimines without additional metal catalyst were not known so far except with Grignard reagent. Triallylaluminum is a useful alternative to provide the homoallylic amines with excellent yield during the reaction with aldimines and ketimines. The significant reactivity of this reagent was proved by reacting with a sterically rigid ketone such as adamantanone to provide 1-adamantyl-3-buten-1-ol in 98% yield. The chemoselectivity of triallylaluminum was demonstrated by taking different ketoesters. The most important thing is triallylaluminum was prepared from allyl bromide and aluminum metal, not from Grignard reagent, and the procedure is operationally simple, with good to excellent product yields. Part Three The use of triallylaluminum in the gem-diallylation of a variety of carboxylic acid derivatives, including acyl azides and halides, is described. Triallylaluminum can be directly prepared from allyl bromide and pure elemental Al, and does not involve a Grignard reagent. The procedure is operationally simple, giving good to excellent product yields for a broad range of substrates. The chemoselectivity and regioselectivity of triallylaluminum was demonstrated via the use of methyl crotonate and cinnamoyl compounds such as cinnamoyl chloride, cinnamoyl azide, methyl cinnamate.三丙烯基鋁試劑( triallylaluminum reagent)丙烯基反應 (allylation reaction)孿位-雙丙烯基反應(gem-diallylation reaction)triallylaluminum reagentallylation reactiongem-diallylation reactionHomoallylic alcoholHomoallylic aminenitrostyrenesnitroalkenes