本文選題：氰基 + 氮雜環(huán)卡賓��； 參考：《貴州大學(xué)》2017年碩士論文

【摘要】：氰基類化合物作為有機合成中的基本合成砌塊廣泛存在于天然產(chǎn)物、醫(yī)藥及農(nóng)藥分子中,如何通過綠色、簡潔、高效的反應(yīng)過程一步構(gòu)建手性氰基類化合物特別是含氰基的手性季碳分子一直是本領(lǐng)域的研究熱點及難點。有機小分子催化劑自從被概念化以后受到了科研人員的廣泛關(guān)注并對其進(jìn)行了深入研究,目前已得到了長足發(fā)展。由于其具有操作簡單、無毒、反應(yīng)條件溫和及后處理簡單等優(yōu)點,已經(jīng)廣泛應(yīng)用于有機合成領(lǐng)域。氮雜環(huán)卡賓(N-heterocyclic carbine,NHC)作為有機小分子催化劑中的后起之秀,由于其獨特的催化活化模式不僅能夠?qū)σ延械姆磻?yīng)進(jìn)行高收率及高立體選擇性控制,而且能夠合成出傳統(tǒng)方法無法合成的結(jié)構(gòu)新穎的新化合物。經(jīng)過近二十年的研究與發(fā)展,目前氮雜環(huán)卡賓催化劑已經(jīng)廣泛應(yīng)用于高效構(gòu)建C-C鍵及C-X(X=O,N,S)鍵并取得了顯著成果。本論文主要研究了利用氮雜環(huán)卡賓為催化劑一步合成含氰基的手性季碳類化合物及初步探討此類化合物的生物活性兩個方面的內(nèi)容。1.利用手性氮雜環(huán)卡賓為催化劑和聯(lián)苯二醌為氧化劑的作用下,催化氧化β-氰基烯醛生成a(11)b-unsaturated acylazolium類中間體,選用1,3-二羰基化合物為親核試劑,在0℃條件下,以四氫呋喃(THF)為溶劑一步合成出具有高收率及高立體選擇性控制的含氰基的手性季碳分子。通過底物拓展我們可以看出此方法對不同取代基取代的β-氰基烯醛類化合物具有很好的普適性,其中部分底物收率可高達(dá)95%,ee值最高可達(dá)98%。我們所用的底物β-氰基烯醛類化合物合成簡單、易得,此方法避免了有毒氰源,如HCN,KCN的使用,為手性氰基類化合物的高效構(gòu)建提供了新策略。2.通過使用濁度法對已合成出的部分目標(biāo)化合物,進(jìn)行生物活性測試。結(jié)果表明,上述化合物對水稻白葉枯病菌基有一定的活性,對煙草青枯病菌基本沒有活性,其中手性化合物化合(R)-ethyl-4-(4-chlorophenyl)-4-cyano-6-methyl-2-oxo-3,4-dihydro-2H-pyran-5-carboxylate在濃度為200μg/m L時對水稻白葉枯病菌的抑制率為90±7.6%,在濃度為100μg/mL時對水稻白葉枯病菌的抑制率為52±6.0%。
[Abstract]:Cyanide compounds are widely used in natural products, medicine and pesticide molecules as basic synthetic blocks in organic synthesis. The synthesis of chiral cyanide compounds, especially the chiral quaternary carbon molecules containing cyanide, has been a hot and difficult point in this field. Since its conceptualization, organic small molecular catalysts have been paid more and more attention by researchers. Because of its advantages of simple operation, non-toxic, mild reaction conditions and simple post-treatment, it has been widely used in the field of organic synthesis. N-heterocyclic carbonic acid (N-heterocyclic carbineHCl) is a rising star in small organic catalyst. Because of its unique catalytic activation mode, it can not only control the reaction with high yield and stereoselectivity, but also can control the reaction in high yield and stereoselectivity. Moreover, new compounds with novel structure can be synthesized which cannot be synthesized by traditional methods. After nearly two decades of research and development, nitrogen heterocyclic carbene catalysts have been widely used in the efficient construction of C-C bonds and C-XOXOON-N (S) bonds, and remarkable results have been obtained. In this paper, the synthesis of chiral quaternary carbohydrates containing cyanide by using heterocyclic carbene as catalyst was studied and the biological activities of these compounds were preliminarily discussed. Using chiral aza-heterocyclic carbene as catalyst and biphenyl diquinone as oxidant, 尾 -cyanenaldehyde was oxidized to form a(11)b-unsaturated acylazolium intermediates, and 1o _ 3-dicarbonyl compound was used as nucleophilic reagent at 0 鈩，

本文編號：1979128