Synthesis Of Chiral Homoallylic Alcohol Compounds By Immobilized Lipase On Magnetic Composite Microsphere

Magnetic polymer microsphere has been widely used in the biomedical field,especially in areas such as immobilized enzyme.In this thesis,we fabricated the microspheres via dispersion polymerization,use a one-pot chemo-enzymatic process to synthesis of chiral homoallylic alcohol compounds.The magnetic polymer microspheres with epoxy groups were successfully synthesized by dispersion polymerization with 2,2-azobisisobutyronitrile(AIBN)as initiator,glycidyl methacrylate(GMA)and styrene(St)as monomers,chitosan modified Fe3O4 nanoparticles as magnetic material and join into monomers without separation and washing.Characterized by SEM,TEM,VSM,XRD,FI-IR,TGA and chemical method,it indicated that the microsphere particle size ranged from 0.8 to 1.4?m,the magnetic polymer microspheres behaved good superparamagnetism.The epoxy functional groups were introduced successfully and the content of epoxy groups is 149.2?mol/g,the saturation magnetization is 13.01emu/g.The racemic 1-(4-methylphenyl)-3-buten-l-ol was synthesised undergo chemical method.Then resolution of 1-(4-methylphenyl)-3-buten-l-ol by enzymatic transesterification was studied while the magnetic polymer microspheres prepared by dispersion polymerization as carriers for preparing immobilized enzyme as catalysts.Optimal conditions were:temperature 40?,vinyl acetate(VA)as acyl donor,the amount of VA were 92 ?L,n-heptane as solvent,99.3%enantiomeric excess(ees)of(S)-1-(4-methylphenyl)-3-buten-l-ol and 96.2%eep of(R)-1-(4-methylphenyl)-3-buten-l-acetate were obtained after 9h.PSL/MP(St-GMA)maintain high catalytic activity under high temperature and and has good storage stability,the ees of(S)-1-(4-methylphenyl)-3-buten-l-ol is 96.8%,the eep of(R)-1-(4-methylphenyl)-3-buten-l-acetate is 98.2%in seven recycling tests.A one-pot chemo-enzymatic process was established to prepare enantiomerically pure(S)-1-(4-chlorophenyl)-3-buten-l-ol.PSL/MP(St-GMA)was selected as catalyst in enzymatic resolution reaction.Under optimal enzymatic resolution reaction conditions,the mass ratio of PSL to MP(St-GMA)was 30 mg:100 mg,temperature 40?,and reaction time 12 h the ee values of substrate(S)-1-(4-chlorophenyl)-3-buten-l-ol,and product(R)-1-(4-chlorophenyl)-3-buten-l-acetate is 99.7%and 95.1%.4-methylbenzaldehyde,Using4-bromobenzaldehyde,4-methoxyzaldehyde,and 3.4-dimethoxyzaldhyde as substrate to synthesis of chiral homoallylic alcohol compounds in one-pot chemo-enzymatic process.Under the optimal conditions for preparation of enantiomerically pure(S)-1-(4-chlorophenyl)-3-buten-l-ol,ten chiral compounds areprepared.The ee values of substrate enantiomers all up to 99%.Using4-bromo-2-thiophenecarboxaldehyde,4-bromo-2-furaldehyde,5-methylfurfural,5-bromo-2-thiophenecarboxaldehyde,5-chloro-2-thiophenecarboxaldehyde as substrate to synthesis of chiral homoallylic alcohol compounds in one-pot chemo-enzymatic process.Under theoptimal conditions for preparation of enantiomerically pure(S)-1-(4-chlorophenyl)-3-buten-l-ol,ten chiral compounds was prepared.The ee values of substrate enantiomers all up to 99%.We established aefficient method which has environment-friendliness,simple technology and high products purity advantages for the preparation of optically purity homoallylic alcohols.