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 

机构地区：[1]Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan,School of Chemistry and Chemical Engineering,Shihezi University,Shihezi 832000,China [2]Hubei Key Lab on Organic and Polymeric Optoelectronic Materials,Engineering Research Center of Organosilicon Compounds&Materials,Ministry of Education,Sauvage Center for Molecular Sciences,Key Laboratory of Biomedical Polymers of Ministry of Education&College of Chemistry and Molecular Sciences,Wuhan University,Wuhan 430072,China

出　　处：《Science China Chemistry》2023年第11期3186-3192,共7页中国科学（化学英文版）

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。

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.

关 键 词：alkynone imine asymmetric hydrogenation propargyl amine ENANTIOSELECTIVITY chiral amine 

分 类 号：O621.251[理学—有机化学] O623.731[理学—化学]