有机-无机杂化载体-聚(苯乙烯-苯乙烯基膦酸)-磷酸氢锆-在烯烃环氧化反应中的应用.pdf

《有机-无机杂化载体-聚(苯乙烯-苯乙烯基膦酸)-磷酸氢锆-在烯烃环氧化反应中的应用.pdf》由会员上传分享，免费在线阅读，更多相关内容在行业资料-天天文库。

1、第28卷第5期无机化学学报V0l_28No．52012年5月CHINESEJOURNALOFINORGANICCHEMISTRY1031—1037有机一无机杂化载体一聚(苯乙烯一苯乙烯基膦酸)一磷酸氢锆在烯烃环氧化反应中的应用邹晓川-，2李俊2石开云2李贵节2傅相锴，-(西南大学化学化工学院应用化学研究所，重庆400715)(重庆教育学院生物与化学工程系，重庆400067)摘要：有机聚合物一无机杂化载体一聚(苯乙烯一苯乙烯基膦酸)一磷酸氢锆一轴向固载手性SalenMn㈣催化剂，将其应用于非官能烯烃的多相不对称环氧化反应

2、。结果表明：在没有昂贵轴向添加剂参与下，产率与对映选择性均急剧增加。以间氯过氧苯甲酸(m—CPBA)为氧化剂催化氧化d—methylstyrene，转化率从25．O％上升到98．8％；对映选择性从5_3％提高到67_3％。催化剂在循环使用5次以后，催化活性无明显改变。关键词：苯氧基修饰聚(苯乙烯基一苯乙烯膦酸)一磷酸氢锆；手性Jacobsen催化剂；非功能化烯烃；不对称非均相环氧化中图分类号：0614．711：0614．41+2：0614．36文献标识码：A文章编号：1001．4861(2012)05—1031．07O

3、rganic-InorganicHybridSupport-ZirconiumPolyrStyrene-Phenylvinylphosphonate)-Phosphate：ApplicationforHeterogeneousOlefinEpoxidationZOUXiao—Chuan，LIJun。SHIKai—YunLIGui—JieFUXiang-Kai'(InstitutleofAppliedemsCollegeofChemistryandChemicalEngineering,SouthwestUniversi

4、ty．Chongqing400715，China)(2DepartmentofBiological&ChemicalEngineering,ChongqingEducationCollege，Chongqing400067，China)Abstract：ThechiralMn(皿salencatalystaxiallyimmobilizedontoanorganic-inorganichybridsuppo~一phenoxymodifiedzirconiumpoly(styrene—phenylvinylph0sph0

5、nate)一phosphate(ZPS—PVPA)canafforddramaticallyincreasedconversionandeefEnantiomericexcess1valueintheabsenceofexpensiveO．coordinatingaxialbasesfortheasymmetricepoxidation．Especiallyfortheepoxidationof—methylstyreneinthem—chloroperbenzoicacid(m—CPBA)oxidantsystem(

6、conv．％：from25．0％to98．8％；ee％：from5．3％to67-3％)．Moreover，theas-synthesizedcatalystisrelativelystableandcanberecycledatleastfivetimeswithoutsignificantlossofactivityandenantioselectivitv．Keywords：phenoxylmodifiedzirconiumpoly(styrene—phenylvinylphosph0nate)一phosphat

7、e；chiraljacobsenshomogenouscatalyst；unfunctionalizedolefins；asymmetricheterogeneousepoxidation0IntroductionagrochemicalfieldstosynthesizechiralbuildingblocksthatcouldbetransformedintootherusefulchiralThechiralMn(1Ⅲ)salencomplexeshaveproventocompoundsthroughregio

8、selectivering—openingbeextremelyeficienthomogeneouscounterpartforreactions【3J．However．separationofsuchhomogeneousasymmetricepoxidationofunfunctionalizedolefins【～．cata