Divergent synthesis of chiral amines via Ni-catalyzed chemo-and enantioselective hydrogenation of alkynone imines

作     者：Yuchuan Ma Kai Liu Lin He Hui Lv 

作者机构：Key Laboratory for Green Processing of Chemical Engineering of Xinjiang BingtuanSchool of Chemistry and Chemical EngineeringShihezi UniversityShihezi 832000China Hubei Key Lab on Organic and Polymeric Optoelectronic MaterialsEngineering Research Center of Organosilicon Compounds&MaterialsMinistry of EducationSauvage Center for Molecular SciencesKey Laboratory of Biomedical Polymers of Ministry of Education&College of Chemistry and Molecular SciencesWuhan UniversityWuhan 430072China 

出 版 物：《Science China Chemistry》 (中国科学(化学英文版))

年 卷 期：2023年第66卷第11期

页      面：3186-3192页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：supported by the National Natural Science Foundation of China (22071188, 21871212) the Open Foundation of CAS Key Laboratory of Molecular Recognition and Function the “Double First-Class” Project of Shihezi University 

主　　题：alkynone imine asymmetric hydrogenation propargyl amine enantioselectivity chiral amine 

摘      要：Ligand-mediated nickel-catalyzed asymmetric hydrogenation of alkynone imines has been achieved. By using Ni(OAc)_2·4H_2O/(S,S)-Ph-BPE complex as a catalyst, the chemo-and enantioselective hydrogenation of alkynone imines occurred efficiently to afford chiral propargyl amines with high yields and excellent enantioselectivities(up to 99% yield, 99% ee), leaving the readily reducible alkynyl group intact. Both the C=N and C≡C bonds of alkynone imines were hydrogenated efficiently in the presence of Ni(OAc)_2·4H_2O and Josiphos SL-J011-1, furnishing unfunctionalized chiral imines efficiently(up to 99% yield, 99% ee).The(Z)-allylamines and(E)-allylamines were also efficiently prepared from alkynone imines by the combination of the different catalytic systems. The preliminary mechanism study revealed that the reduction of alkynone imines was a stepwise process and the C=N bonds were preferably hydrogenated in the complete reduction of alkynone imines. The synthetic utility of this method was demonstrated by its application in the late-stage modification of the antiviral drug Zidovudine and the concise synthesis of chiral dibenzoazepine.