【摘要】：隨著過渡金屬催化C-N鍵偶聯(lián)反應的發(fā)展,涌現(xiàn)了許多N-芳基酰胺化合物的合成方法。相比之下,鹵代芳烴的酰胺化反應通常面臨著鹵素取代的底物不兼容的問題,而簡單芳烴的C-H鍵酰胺化反應往往面臨選擇性、需預官能團化、不得不采用特殊芳烴以及貧電子芳烴不兼容的缺點。能否以一種高效可控、符合原子經(jīng)濟性的方法來有效構(gòu)建酰胺鍵,這對于藥物以及天然產(chǎn)物中間體的合成具有重大的意義。除此之外,芳烴C-H鍵選擇性氧化也是近年來的研究熱點之一,如何在活化芳烴C-H鍵的同時實現(xiàn)其區(qū)域選擇性的控制,確實面臨著不小的挑戰(zhàn)。除了特殊取代的芳烴如苯酚和苯酰胺類能實現(xiàn)對位C-H鍵選擇性氧化之外,簡單芳烴直接氧化通常會面臨選擇性的問題。另一種則是采取螯合輔助的方式,該方法雖然有效,但芳烴需要進行額外的官能團化,使得其在實用性方面受到一定的限制。本論文主要分為以下兩部分:第一章,我們利用腈對芳基硼酸的酰胺化反應,發(fā)展了一種高效合成N-芳基酰胺的方法。該體系底物范圍廣,不僅能夠同時兼容富電子官能團、貧電子官能團,而且也能適用于鹵代取代的底物。第二章,我們發(fā)展了一種富電子芳烴/雜環(huán)芳烴區(qū)域選擇性的C-H鍵磺酰氧化反應,電子效應和位阻效應使得磺酰氧化在富電子芳烴/雜環(huán)芳烴的特定位置發(fā)生。不僅如此,磺酰氧化后的產(chǎn)物能用于水解成酚,并且還可以作為親電試劑應用于偶聯(lián)反應中,大大拓寬了反應底物的應用范圍。綜上所述,本文發(fā)展了一種新的合成N-芳基酰胺的方法,高效制備了各種取代的N-芳基酰胺化合物,改善了反應的官能團兼容性,拓寬了底物范圍。針對富電子芳烴C-H鍵氧化選擇性難的問題,本文還發(fā)展了一種可控高效的方法,實現(xiàn)了富電子芳烴/雜環(huán)芳烴的區(qū)域選擇性C-H鍵磺酰氧化反應。
[Abstract]:With the development of transition metal catalyzed C-N bond coupling reaction, many synthesis methods of N-aryl amides have emerged. In contrast, the amidation reaction of halogenated aromatics usually faces the problem of incompatibility of halogen-substituted substrates, while the C-H bond amidation of simple aromatics often faces selectivity and requires prefunctionalization. The disadvantage of having to use special aromatics and poor electronic aromatics is incompatibility. It is of great significance for the synthesis of drugs and intermediates of natural products to construct the amide bond effectively by a highly efficient and controllable method which accords with the atomic economy. In addition, the selective oxidation of aromatic C-H bond is one of the hot topics in recent years. How to activate the C-H bond of aromatics at the same time to realize the control of its regioselectivity is a real challenge. In addition to the selective oxidation of special substituted aromatics such as phenol and benzamide, the direct oxidation of simple aromatics usually faces the problem of selectivity. The other is chelating assisted method. Although the method is effective, the aromatics need additional functionalization, which makes it limited in practicability. This thesis is divided into two parts as follows: in Chapter 1, we developed an efficient method for the synthesis of N-aryl amide by amidation of nitrile to aryl boric acid. The system has a wide range of substrates, which can not only be compatible with electron-rich functional groups and poor electronic functional groups at the same time, but also suitable for halogenated substrates. In chapter 2, we develop a regioselective C-H bond oxidation reaction of electron-rich aromatics / heterocyclic aromatics. The electron effect and steric effect make the oxidation of sulfonyl occur in the specific position of electron-rich aromatics / heterocyclic aromatics. Moreover, the sulfonyl oxidized products can be used to hydrolyze phenol and can be used as electrophilic reagents in coupling reactions, which greatly broadens the application range of reaction substrates. In conclusion, a new method for the synthesis of N-aryl amides has been developed in this paper. Various substituted N-aryl amides have been synthesized efficiently, which improves the functional compatibility of the reaction and broadens the substrate range. Aiming at the difficulty of C-H bond oxidation selectivity of electron-rich aromatics, a controllable and efficient method has been developed to realize the regioselective C-H bond sulfonyl oxidation of electron-rich aromatics / heterocyclic aromatics.
【學位授予單位】：四川師范大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O621.251

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相關(guān)期刊論文 前1條

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本文編號：2353185