手性亚磷酰胺酯铱络合物催化的喹啉的不对称氢化反应  

Asymmetric hydrogenation of quinolines catalyzed by phosphoramidites iridium complexes

作　　者：丰检 肖祥辉 王大寒 张凤[1] FENG Jian;XIAO Xianghui;WANG Dahan;ZHANG Feng(School of Chemistry and Materials Science, Hunan Agricultural University, Changsha 410128, China)

机构地区：[1]湖南农业大学化学与材料科学学院,湖南长沙410128

出　　处：《湘潭大学学报（自然科学版）》2022年第1期41-52,共12页Journal of Xiangtan University(Natural Science Edition)

基　　金：国家自然科学基金(21302051);第12批中国博士后科学基金特别资助(站中)(2019T120709)。

摘　　要：喹啉的不对称氢化反应是制备重要有机合成中间体手性四氢喹啉最高效的方法之一.该文通过两步反应合成了亚磷酰胺酯配体,配体结构经过了氢谱、碳谱、磷谱以及高分辨质谱的表征.将亚磷酰胺酯配体用于铱催化的2-甲基喹啉的不对称氢化反应中,研究结果表明:采用富电子的亚磷酰胺酯作为配体,四氢呋喃作为溶剂,通过添加哌啶盐酸盐及三(邻甲基苯基)磷,产物的对映选择性能提升到90%.在最优反应条件下,喹啉衍生物均能以较高产率及中等到较高对映选择性(最高达91%)顺利生成目标产物.Asymmetric hydrogenation represents one of the most effective methods for the preparation of the important synthetic intermediates-chiral tetrahydroquinolines.The monodentate phosphoramidites were synthesized via two-step reaction,and characterized by ^(1)H NMR,^(13)C NMR,^(31)P NMR and HRMS.The ligands were applied to the iridium-catalyzed asymmetric hydrogenation of 2-methylquinoline,the results demonstrated that when electron-rich phosphoramidite was uesd as the ligand,THF as solvent,piperidinechloride salt and tri(orthotolyl)phosphine as additives,enantioselectivities were greatly enhanced up to 90%.Under the optimal conditions,the substrate scope can be expanded to the quinoline derivatives,all the tested substrates were smoothly converted to target products with good yields and moderate to good enantioselectivities(up to 91%ee).

关 键 词：手性四氢喹啉 不对称氢化 亚磷酸酰胺酯 铱 

分 类 号：O621[理学—有机化学]