手性氮膦配体在不对称烯丙基化反应和Suzuki偶联反应中的应用

发布时间：2018-05-09 08:01

本文选题：手性氮膦配体 + 不对称催化　；参考：《宁波大学》2017年硕士论文

【摘要】：过渡金属催化反应在有机合成领域中有着极其广泛的应用,通过该类型反应可以构建碳氢、碳碳、碳氮、碳氧、碳硫等键,可以合成多种复杂的活性药物中间体和手性有机分子。在过渡金属催化反应中,手性氮膦配体的应用一直是研究的重点。设计合成出一种结构新颖、容易制备、高活性的氮膦配体,且能与过渡金属螯合来催化反应时具备高选择性,仍然是一个具有挑战性的难题。本论文针对这一难题,展开了研究工作,合成了一类以天然樟脑为主要骨架的手性氮膦配体,并研究了其在不对称催化烯丙基化反应和Suzuki偶联反应中的应用。我们以商业化的天然樟脑为手性源,并运用模块化的概念,通过简单的修饰与偶联合成了一类新型的手性氮膦配体。该手性氮膦配体保留了天然樟脑的刚性骨架结构,而且原料易得、易于合成,在空气中稳定。同时我们研究了其与过渡金属钯螯合,不对称催化烯丙基化反应和Suzuki偶联反应。研究表明,由天然樟脑衍生的新型席夫碱类化合物是一类高效的氮膦配体,能够有效催化吲哚类的不对称烯丙基化反应,表现出卓越的催化性能,以良好的产率(高达92%yield)和优秀的对映选择性(高达98%ee)得到多种手性产物。手性氮膦配体在催化大位阻Suzuki偶联反应中,表现出优越的催化性能,最高以97%yield得到偶联产物。说明了刚性的天然樟脑骨架结构在该类配体中起着重要的作用。
[Abstract]:Transition metal catalytic reactions are widely used in the field of organic synthesis, through which bonds such as carbon, carbon, carbon and nitrogen, carbon and oxygen, carbon and sulfur can be constructed. Many complex active drug intermediates and chiral organic molecules can be synthesized. The application of chiral nitrogen-phosphine ligands in transition metal catalytic reactions has been the focus of research. It is still a challenging problem to design and synthesize a novel, easily prepared, highly active nitrophosphine ligand with high selectivity for catalytic reaction with transition metal chelation. In order to solve this problem, a class of chiral nitrophosphine ligands with natural camphor as the main skeleton were synthesized and their applications in asymmetric allylation and Suzuki coupling reactions were studied. Using commercial natural camphor as chiral source and using the concept of modularization, a novel chiral nitrophosphine ligands were synthesized by simple modification and coupling. The chiral nitrophosphine ligands retain the rigid skeleton structure of natural camphor, and the raw materials are easy to be obtained, easy to synthesize and stable in air. At the same time, we studied their chelation with transition metal palladium, asymmetric allylation and Suzuki coupling reaction. The results show that the novel Schiff base compounds derived from natural camphor are a class of highly efficient nitrophosphine ligands, which can effectively catalyze the asymmetric allylation of indole and exhibit excellent catalytic performance. A variety of chiral products were obtained with good yield (up to 92 yield) and excellent enantioselectivity (up to 98). Chiral nitrophosphine ligands showed excellent catalytic performance in the large steric barrier Suzuki coupling reaction, and the coupling products were obtained by 97%yield. It is concluded that rigid natural camphor skeleton plays an important role in this kind of ligand.
【学位授予单位】：宁波大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.25

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