【摘要】：氫鍵是一種重要的非共價鍵相互作用,在不對稱合成以及氫鍵催化等方面得到了廣泛應用。鹵鍵和氫鍵很相似,相比于氫鍵,鹵鍵具有其獨特的優(yōu)點。例如,良好的方向性(鹵鍵的鍵角接近180°),更強的相互作用以及更大的原子尺寸等。但是到目前為止鹵鍵在有機合成中的應用遠少于氫鍵的。尋求鹵鍵的應用已經(jīng)成為當下有機合成領域的重要研究課題。本文的工作是探索通過鹵鍵作用來實現(xiàn)對亞砜化合物的活化,然后通過Pummerer重排反應,合成目標產(chǎn)物。(一)我們從常用的溴代試劑NBS出發(fā),實現(xiàn)了對DMSO(二甲基亞砜)的直接活化,通過引入外加胺(鄰苯二甲酰亞胺、磺酰胺、苯駢三氮唑等)后,生成還原胺化產(chǎn)物(氮硫縮醛產(chǎn)物)；從NBP、 NCP、N-溴代糖精出發(fā)則可以直接與DMSO生成還原胺化產(chǎn)物。機理研究表明：首先,N-溴代酰亞胺中的溴和DMSO中的氧能夠產(chǎn)生鹵鍵作用,加熱后溴原子轉(zhuǎn)移到DMSO的氧上生成了溴氧鍵；然后,經(jīng)由脫去次溴酸生成硫摀離子,在親核進攻下生成還原胺化產(chǎn)物。(二)在NBS活化的二芐基亞砜中加入胺后會發(fā)生Interrupted Pummerer重排反應,實現(xiàn)了氮硫原子的直接成鍵；NBP與二芐基亞砜反應也可以得到氮硫原子直接成鍵的產(chǎn)物。盡管在NBS活化的效率以及親核試劑的適用范圍上仍存在不足,但在鹵鍵活化領域仍具有其現(xiàn)實和理論意義：拓寬了Pummerer重排反應的發(fā)展道路,開辟了NBS新用途,豐富了鹵鍵的應用。
[Abstract]:Hydrogen bond is an important noncovalent bond interaction and has been widely used in asymmetric synthesis and hydrogen bond catalysis. Halogen bond and hydrogen bond are very similar, compared with hydrogen bond, halogen bond has its unique advantages. For example, good directionality (the bond angle of halogen bond is close to 180 擄), stronger interaction and larger atomic size, etc. But so far halogen bonds have been used in organic synthesis much less than hydrogen bonds. The application of halogen bond has become an important research topic in the field of organic synthesis. The work of this paper is to explore the activation of sulfoxide by halogenation, and then to synthesize the target product by Pummerer rearrangement reaction. (1) We have realized the direct activation of DMSO (dimethyl sulfoxide) from the commonly used brominated reagent NBS. After the addition of amine (phthalimide, sulfonamide, benzotriazole, etc.), The reductive amination product (azo acetal product) was formed, and the reductive amination product could be obtained from NBP, NCPN brominated saccharin and DMSO directly. The mechanism study shows that: first, bromine in N-bromoimide and oxygen in DMSO can produce halogen bond, and the bromoxide atoms transfer to the oxygen of DMSO to form bromo-oxygen bond after heating. Under nucleophilic attack, reductive amination products were formed. (2) the interrupted Pummerer rearrangement reaction will take place after the addition of amine into the NBS activated dibenzyl sulfoxide, and the direct bond formation reaction between NBP and dibenzyl sulfoxide can also be achieved. Although the efficiency of NBS activation and the application range of nucleophilic reagents are still insufficient, it still has practical and theoretical significance in the field of brine bond activation: it broadens the development path of Pummerer rearrangement reaction and opens up a new application of NBS. Enriched the application of halogen bond.
【學位授予單位】：東北師范大學
【學位級別】：碩士
【學位授予年份】：2016
【分類號】：O621.254.2

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