Chiral Diamine Oxime Tandem Michael Addition And Asymmetric Hydrogen Transfer Catalyzed Synthesis Of ?-amino Alcohol

As we know,?-amino alcohol structural motifs are embedded in a wide range of natural products and biologically active compounds.The ?-Amino alcohols were widely used as ligands and pharmaceutical intermediates,especial in the syntheses of many important drugs.Classical synthetic approach to ?-amino alcohol unit is asymmetric-restore product which comes from the Mannich-type reaction.Compared with it,herein we get ?-amino alcohol unit by string aza-Michael reaction and asymmetric hydrogen transfer reac tion.It contains aza-Michael reaction which a general,efficient and environmentally friendly reaction.Another hand,asymmetric hydrogen transfer reaction happened at room temperature and atmospheric pressure.This paper is divided into the following two parts.First: Aza-Michael–Asymmetric transfer hydrogenation tandem one-pot reaction to ?-amino alcohol through ruthenium: With 1-phenylprop-2-en-1-one and aniline as the raw material to synthesize ?-amino alcohol,we optimize the reaction conditions and catalysts.We found that RuCl[(S,S)-Ts DPEN](mesitylene)was the best chiral catalyst and sodium formate as the hydrogen source.We successfully synthesize higher yield and enantiomeric selective of chiral ?-amino alcohols in mix-solvent 0.1 mol/L sodium carbonate with isopropanol in a volume ratio of 1: 1,at 40 °C.The catalyst has fine substrate applicability.We had been synthesis a series of derivative compounds for the chiral ?-amino alcohol and achieved a fine result in both selectivity and yield.Second: Synthesis of ?-amino alcohols by core-shell functional supported chiral catalytic: Combination of 1,4-diazabicyclo [2.2.2] octane in Aza-Michael reaction,we want to get ?-amino alcohols by 1,4-diazabicyclo [2.2.2] octane,but it not succeed.We found the 1,4-diazabicyclo [2.2.2] influence the process of catalyzing.In the context of green chemistry,taking into account the adverse effects of DABCO on asymmetric hydrogen transfer catalysts,shell mesoporous silicon material is my favorite.We use tetraethylorthylorthosilicatr and 1,2-bis(triethoxysily)ethane as the framework of the core-shell materials.By then use 1-(2-(triethoxysilyl)ethyl)-1,4-dia zabicyclo[2.2.2]octan-1-iumchloride and(1S,2S)-4-(trimethoxysilyl)ethyl)phenylsulf onyl-1,2-diphenylethylenediamine as functional of the core-shell materials.We were successfully prepared IT-DABCO@ArDPEN@MNPs core-shell functional materials through hydrolysis copoly-merization.The 1,3,5-trimethylphenyl ruthenium chloride dimer was successfully implanted in the core of the core-shell material.The catalyst was successfully supported and catalyzed by 13 CCP / MAS NMR,XPS,29 Si MAS NMR and IR.The morphology,specific surface area,pore size,metal content and distribution of the catalyst were observed by SEM,TEM,BET,XRD.We successfully apply it in series of Aza-Michael and asymmetric hydrogen transfer to one-pot synthesis of chiral ?-amino alcohols.We found to have good results in stereoselectivity and yield,with 99% of the best enantio-selectivity,yield 86%.A series of different chiral ?-amino alcohols was synthesized by expanding the 17 substrates.We found the catalyst could be recycled.