本文選題：酮酸 + β-酮酸　； 參考：《合肥工業(yè)大學》2017年博士論文

【摘要】：竣酸作為一種廉價易得的化合物在有機合成中一直被研究人員廣泛研究。近來報道了一種用芳基羧酸作為底物的脫羧反應,得到產(chǎn)物與Heck反應的產(chǎn)物一樣,這種脫羧反應被報道以后,利用過渡金屬作為催化劑的脫羧偶聯(lián)反應逐漸引起了人們的興趣,并慢慢成為目前的一個研究熱點。在合成具有非平面結(jié)構(gòu)的有機分子時,過渡金屬催化的烷基偶聯(lián)反應具有重要的意義,所以過渡金屬催化的烷基羧酸的脫羧偶聯(lián)反應也得到了科學家們的廣泛重視。光催化的偶聯(lián)反應近年來得到了廣泛的關注,可見光催化的反應體系也為脫羧偶聯(lián)反應提供了新的思路,最近很多利用光催化的脫羧偶聯(lián)反應被報道出來。在第一章中,我們分別從過渡金屬和光催化的脫羧偶聯(lián)反應對前人的工作進行了總結(jié)。酰胺鍵作為蛋白質(zhì)的基本構(gòu)建骨架,在生命中扮演著重要角色,同時大量存在于各種生物質(zhì)材料和藥物活性分子中。目前公認最常用的策略就是胺的乙�；磻�。雖然制備酰胺最普遍簡單的方法是通過羧酸與胺的縮合。但是這個最理想的策略需要極其苛刻的條件,比如高溫條件,并且在形成酰胺鍵過程中不可避免的經(jīng)過羧酸銨鹽副反應。在第二章中我們介紹了一種Ag催化的羧酸脫酸酰胺化的反應。反應在空氣條件下進行,反應條件也很溫和,用α-酮酸作為底物與胺發(fā)生脫羧酰胺化合成酰胺。反應的產(chǎn)率較好,而且顯示出優(yōu)異的官能團耐受性。而且將底物的胺換成二氨基化合物以后可以進一步得到雜環(huán)化合物如苯并咪唑的產(chǎn)物。藥物分子中含有三氟甲基可以有效改善其親脂性、可吸收性以及代謝穩(wěn)定性。因此,在有機分子中引入三氟甲基引起了人們的廣泛關注。三氟甲基引入到有機分子中的方法有很多報道。然而,C(sp3)上引入三氟甲基與C(sp2)-CF3和C(sp)-CF3相比明顯研究較少。近期在這個領域中用烷基鹵化物、烷基硅烷、炔烴和烷基硼酸作為底物的三氟甲基化反應已經(jīng)被報道。最近,過渡金屬催化的三氟甲基化反應得到了快速發(fā)展。其中,Cu作為一種廉價且活性較高的催化劑能夠?qū)崿F(xiàn)多種三氟甲基化反應。在第三章中我們開發(fā)了一種有效的β-酮酸脫羧三氟甲基化得到α-三氟甲基酮的方法。這個反應使用Cu鹽作為過渡金屬催化劑,在室溫下就可以進行,而且得到的產(chǎn)物產(chǎn)率較好。此外這個脫羧三氟甲基化的反應體系兼容性也很好,很多富電子和缺電子的底物都能順利參與反應,得到相應的α-三氟甲基酮。
[Abstract]:As a cheap and readily available compound, dioxic acid has been widely studied in organic synthesis. Recently, a decarboxylation reaction using aryl carboxylic acid as substrate has been reported. The product is similar to that of Heck reaction. After this decarboxylation reaction is reported, the decarboxylation coupling reaction using transition metal as catalyst has gradually attracted people's interest. And gradually become a research hotspot. In the synthesis of organic molecules with non-planar structure, transition metal-catalyzed alkyl coupling reaction is of great significance, so transition metal-catalyzed decarboxylation of alkyl carboxylic acids has been paid more and more attention by scientists. Photocatalytic coupling reactions have been paid more and more attention in recent years. The visible photocatalytic reaction system has also provided a new way of thinking for decarboxylation. Recently, many photocatalytic decarboxylation coupling reactions have been reported. In the first chapter, we summarized the previous work from transition metal and photocatalytic decarboxylation coupling reaction. As the basic framework of protein, amide bond plays an important role in life, and it also exists in a variety of biomaterials and pharmaceutical active molecules. The most commonly used strategy is the acetylation of amines. Although the simplest way to prepare amides is by condensation of carboxylic acids with amines. However, this optimal strategy requires extremely harsh conditions, such as high temperature conditions, and the formation of amide bonds is inevitable through carboxylate side reactions. In chapter 2, we introduce a Ag-catalyzed deacidification and amidation of carboxylic acid. The reaction was carried out in air, and the reaction conditions were very mild. 偽 -ketoic acid was used as substrate to decarboxylation with amine to synthesize amides. The yield of the reaction was good and showed excellent functional group tolerance. The heterocyclic compounds such as benzimidazole can be further obtained by replacing the amines of the substrate with diamino compounds. Trifluoromethyl can effectively improve lipophilic, absorbability and metabolic stability. Therefore, the introduction of trifluoromethyl in organic molecules has attracted widespread attention. The introduction of trifluoromethyl into organic molecules has been widely reported. However, compared with C(sp2)-CF3 and C(sp)-CF3, the study of introducing trifluoromethyl into Cesp 3 is much less. Recently, trifluoromethylation of alkyl halides, alkyl silanes, alkynes and alkyl boric acids has been reported in this field. Recently, transition metal catalyzed trifluoromethylation has developed rapidly. Cu as a cheap and highly active catalyst can realize various trifluoromethylation reactions. In Chapter 3, we developed an effective method for the synthesis of 偽 -trifluoromethyl ketone by decarboxylation of 尾 -ketoic acid with trifluoromethyl methylation. This reaction can be carried out at room temperature using Cu salt as transition metal catalyst and the yield of the product is better. In addition, the reaction system of decarboxyltrifluoromethylation is also very compatible, and many electron-rich and electron-deficient substrates can participate in the reaction successfully to obtain the corresponding 偽 -trifluoromethyl ketones.
【學位授予單位】：合肥工業(yè)大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：O621.251

【參考文獻】

相關期刊論文 前1條

1 ;Transition metal-catalyzed decarboxylative cross-coupling reactions[J];Science China(Chemistry);2011年11期

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本文編號：1951321