PNA的合成以及相应杂合催化剂配体的构建

发布时间：2018-06-21 04:05

本文选题：PNA + 杂合催化剂　；参考：《北京化工大学》2017年硕士论文

【摘要】：肽核酸(PNA)是一种寡核苷酸类似物,由于性质优良,已经被应用于多个领域,如分子生物学工具等等,目前甚至有人认为PNA与生命起源有关。以手性生物大分子为基础构建的手性催化剂是近年来手性催化研究的热点方向之一,目前研究较为成熟的是以DNA为基础的杂合催化剂,因其本身的手性环境等特点可以达到为理想的催化效率,寻找合适的配体分子是解释其催化机理,构建新型杂合催化剂的关键所在,而PNA还尚未应用到这个领域。本文从PNA的合成出发,采用Boc/Z保护基策略,合成出了骨架和四种碱基的羧酸衍生物,并通过酰胺缩合的办法将骨架与羧酸衍生物连接,合成出了四个PNA单体。其中T单体的合成需3步反应,A、C两种单体各需要4步反应,而较为复杂的G单体则经过6步反应合成单体,本文也对其的合成路径进行了初步的优化。在完成了 4个单体的合成之后,我们分别尝试了 PNA的固相合成和液相合成,并最终选择液相合成的办法合成PNA短链2T以及3T,至此完成了 PNA部分的合成工作。本文还合成了联吡啶羧酸,并且将联吡啶羧酸与PNA的T单体以及T二聚体的N端以酰胺缩合的方式连接,成功构建出了相应DNA杂合催化剂初步的新配体,对杂合催化剂中立体选择性产生的原理的探究具有重要意义。
[Abstract]:Peptide nucleic acid (PNA) is a kind of oligonucleotide analogue which has been used in many fields such as molecular biological tools because of its excellent properties. At present some people even think that PNA is related to the origin of life. Chiral catalysts based on chiral macromolecules are one of the hot topics in recent years. Because of its chiral environment and other characteristics can achieve ideal catalytic efficiency, finding suitable ligands is the key to explain its catalytic mechanism and construct a new hybrid catalyst, but PNA has not yet been applied to this field. Starting from the synthesis of PNA, four carboxylic acid derivatives of skeleton and four bases were synthesized by using Boc-Z protection group strategy, and four PNA monomers were synthesized by linking the skeleton with carboxylic acid derivatives by amide condensation. The synthesis of T monomer requires 4 steps each of the two monomers, while the more complex G monomer needs 6 steps to synthesize monomer. The synthesis path of T monomer is also preliminarily optimized in this paper. After the synthesis of four monomers, we tried the solid-phase synthesis and liquid-phase synthesis of PNA, and finally selected the method of liquid-phase synthesis to synthesize PNA short chain 2T and 3T, so as to complete the synthesis of PNA. Bipyridine carboxylic acid was also synthesized, and the N-terminal of PNA and T dimer was connected with bipyridine-carboxylic acid in the form of amide condensation, and a new ligand of corresponding DNA hybrid catalyst was successfully constructed. It is of great significance to explore the principle of stereoselectivity in hybrid catalysts.
【学位授予单位】：北京化工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.3;O643.36

【相似文献】