经由卤键活化的亚砜的还原胺化反应
发布时间：2018-07-20 17:45
【摘要】：氢键是一种重要的非共价键相互作用,在不对称合成以及氢键催化等方面得到了广泛应用。卤键和氢键很相似,相比于氢键,卤键具有其独特的优点。例如,良好的方向性(卤键的键角接近180°),更强的相互作用以及更大的原子尺寸等。但是到目前为止卤键在有机合成中的应用远少于氢键的。寻求卤键的应用已经成为当下有机合成领域的重要研究课题。本文的工作是探索通过卤键作用来实现对亚砜化合物的活化,然后通过Pummerer重排反应,合成目标产物。(一)我们从常用的溴代试剂NBS出发,实现了对DMSO(二甲基亚砜)的直接活化,通过引入外加胺(邻苯二甲酰亚胺、磺酰胺、苯骈三氮唑等)后,生成还原胺化产物(氮硫缩醛产物)；从NBP、 NCP、N-溴代糖精出发则可以直接与DMSO生成还原胺化产物。机理研究表明：首先,N-溴代酰亚胺中的溴和DMSO中的氧能够产生卤键作用,加热后溴原子转移到DMSO的氧上生成了溴氧键；然后,经由脱去次溴酸生成硫摀离子,在亲核进攻下生成还原胺化产物。(二)在NBS活化的二苄基亚砜中加入胺后会发生Interrupted Pummerer重排反应,实现了氮硫原子的直接成键；NBP与二苄基亚砜反应也可以得到氮硫原子直接成键的产物。尽管在NBS活化的效率以及亲核试剂的适用范围上仍存在不足,但在卤键活化领域仍具有其现实和理论意义：拓宽了Pummerer重排反应的发展道路,开辟了NBS新用途,丰富了卤键的应用。
[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 掳), 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.
【学位授予单位】：东北师范大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.254.2
本文编号：2134274
[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 掳), 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.
【学位授予单位】：东北师范大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.254.2
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