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1、面包酵母生物催化不對稱合成丹參素冰片酯匡新謀1,孫穎2,白亞軍2,南葉飛3,鄭曉暉2*(1寧波職業(yè)技術(shù)學(xué)院化工學(xué)院,浙江寧波,315800;2西北大學(xué)生命科學(xué)學(xué)院,陜西西安,710069;3西安石油大學(xué)化學(xué)化工學(xué)院,陜西西安,710065)摘要:本文以3,4-二羥基苯甲醛為原料,經(jīng)Knoevenagel縮合、水解反應(yīng)合成β-(3,4-二羥基苯基)丙酮酸,利用對甲基苯磺酸催化β-(3,4-二羥基苯基)丙酮酸和冰片反應(yīng)合成了β-(3,4-二羥基苯基)丙酮酸冰片酯,最后利用面包酵母生物催化不對稱合成了丹參素冰片酯(DBZ)。系統(tǒng)考察了葡萄糖加入量、反應(yīng)時間、pH及β
2、-環(huán)糊精加入量等因素對面包酵母生物催化合成不對稱丹參素冰片酯的影響,結(jié)果表明:在底物β-(3,4-二羥基苯基)丙酮酸冰片酯加入量為0.5g時,其最佳反應(yīng)條件為:葡萄糖30g、β-環(huán)糊精1.5g、pH為7、反應(yīng)時間24h,此條件下對映體過量值(ee值)高達(dá)84.9%,產(chǎn)物主要為S構(gòu)型的丹參素冰片酯。該工藝條件溫和、成本較低,是一條極具價值的丹參素冰片酯生產(chǎn)工藝。關(guān)鍵詞:面包酵母;生物催化;不對稱還原;β-環(huán)糊精;丹參素冰片酯StudyonBiosynthesisofAsymmetricSyntheticDanshensuBorneolesterbyBaker's
3、Yeast(KUANGXin-mou1,SUNYing2,BAIYa-jun2,NANYe-fei3,ZHENGXiao-hui2)(1Schoolofchemicalengineering,NingboNingboPolytechnic,Ningbo315800,ZheJiang,China;2CollegeofLifeSciences,NorthwestUniversity,Xi'an710069,ShanXi,China;3CollegeofChemistryandChemicalEngineering,Xi’anShiyouUniversity,Xi’
4、an710065,ShanXi,China)Abstract:Inviewofthedisadvantagesofhighcost、hashexperimentalconditionsandlowutilizationrateofrawmaterialsinexistingreports.Inthepaper,3,4-dihydroxybenzaldehydewasusedasrawmaterial,refertotheliteraturemethod,andβ-(3,4-dihydroxyphenyl)pyruvateborneolesterwassynth
5、esizedatfirst,thenunderthebread’syeastfermentationliquidandtargetproductDanshensuborneolesterwassynthesized.Theinfluenceofamountofglucoseandβ-cyclodextrin、reactiontime、pHwereinvestigatedinthepaper.Whenβ-(3,4-dihydroxyphenyl)pyruvateborneolesterwas0.5g,Andthebestconditionswereasfollo
6、w:amountofglucosewas30g,reactiontimewas24h,pHwas7,amountofβ-cyclodextrinwas1.5g.enantiomericexcessvalveofthetargetproductashighas84.9%,andmainconfigurationwasS-DBZ.Thereactionconditionsoftheprocessinthispaperweremildandthecostwaslow,whichwasaveryvaluableprocessfortheproductionofDans
7、hensuborneolester.Keyword:Baker'syeast;Biocatalytic;asymmetricreduction;β-(3,4-dihydroxyphenyl)pyruvateborneolester;DanshensuBorneolEster基金項目:1超臨界流體色譜的開發(fā)與應(yīng)用(2013YQ170525;子項目:超臨界流體色譜在中藥及其代謝物中的應(yīng)用研究,2013YQ17052509);2中國長江學(xué)者課程和教育部大學(xué)創(chuàng)新研究團(tuán)隊(IRT_15R55)Foundationitem:1The?Development?and?App
8、lication?of?Supercr