新型手性醛催化剂的设计合成与应用研究

发布时间：2018-08-19 13:47

【摘要】：发展新型手性有机催化剂是不对称有机合成的重要研究方向。本文设计合成了系列联二萘酚及螺环二酚衍生的手性醛催化剂,并对其催化性能和立体控制效果进行了详细探讨。本文第一部分概述了醛作为辅基参与有机化学转化,其次阐述了手性醛作为催化剂催化的不对称有机反应,包括:环状脂肪族手性醛作为“tethering catalyst”催化烯烃发生分子间的Cope-type氢胺化反应;手性吡哆醛催化ɑ-酮酸的不对称转胺化反应;以及手性醛催化氨基丙二酸酯的ɑ-烷基化反应。本文第二部分在前人工作基础上,通过对催化剂3-位和6,6’-位取代基的调节来实现手性醛催化剂位阻效应和电子效应的改变,以及催化位点位置的改变来拉近和催化剂手性中心的距离,合成了BINOL衍生的手性醛催化剂;并依据螺环二酚骨架的特性,合成了SPINOL衍生的手性醛催化剂。将这些催化剂应用于氮上未保护的氨基丙二酸酯直接的不对称ɑ-烷基化反应中,获得了高达84%的收率以及87%的对映选择性。本文第三部分详细描述了系列手性醛化合物的合成步骤,并提供了其1H-NMR、13C-NMR及高分辨质谱等表征数据。
[Abstract]:The development of novel chiral organic catalysts is an important research direction in asymmetric organic synthesis. A series of chiral aldehydes derived from binaphthol and spirodiol have been designed and synthesized, and their catalytic properties and stereoscopic control effects have been discussed in detail. In the first part of this paper, aldehydes as an auxiliary group in organic chemical transformation are summarized, and chiral aldehydes as catalysts for asymmetric organic reactions are described. It includes: cyclic aliphatic chiral as "tethering catalyst" catalyzed Cope-type hydroamination of olefins; chiral pyridoxal catalyzed asymmetric transamination of ketoic acid; and chiral aldehyde-catalyzed N-alkylation of aminomalonic acid ester. In the second part of this paper, the steric and electronic effects of chiral aldehydes are changed by adjusting the substitution groups of 3- and 6-, 6- and 6-, and the electronic effect of the chiral aldehydes is changed on the basis of the previous work. The chiral aldehyde catalyst derived from BINOL was synthesized by changing the position of catalytic site to shorten the distance between the chiral center of the catalyst and the chiral center of the catalyst, and the chiral aldehyde catalyst derived from SPINOL was synthesized according to the characteristics of the spirocyclic diphenol skeleton. These catalysts were applied to direct asymmetric alkylation of unprotected amino malonates on nitrogen with a yield of up to 84% and enantioselectivity of 87%. In the third part, the synthetic steps of a series of chiral aldehydes are described in detail, and their 1H-NMR13C-NMR and high resolution mass spectra are provided.
【学位授予单位】：西南大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36;O622.4

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