天然和修饰环糊精的不对称光化学

用修饰的α-，β-，γ-环糊精(CDs)的包结增感作用研究(Z)-环辛烯(1Z)向手性(E)-异构体(1E)的超分子对映差向光异构反应。建立定量圆二色(CD)和差圆二色(DCD)公式,研究修饰α-，β-，γ-环糊精衍生物与1Z包结反应的构象、化学量和稳定常数。实验发现结合诱导的CD光谱变化是温度和修饰环糊精浓度的临界函数。同时发现光稳态E/Z随照射时间增长而增加最后达到光稳定状态,但明显依赖于增感剂结构和溶液中甲醇含量，它与环糊精手性空腔被客体1Z占有率有直接关系。考查含o-,m-,p-羧酸甲酯基团的苯甲酸β-环糊精酯衍生物的光增感和对映差向能力，更好地认识到在CDs空腔内的有效光能转换是怎样发生的。用邻苯二甲酸β-环糊精酯的对映体过剩（ee）从2.9%增加到24%。有趣的是产物的ee值与取代基常数（Hammett,σ）间没有明显的关系，却与某些苯甲酸β-CD酯的主体占有率有直接关系，即是通过分析在不同甲醇含量的水溶液中被一些β-CD衍生物增感的对映差向光异构反应中的ee，得出被底物1Z占有主体空腔的百分率。[1]InoueY.Chem.Rev.,1992,92741—770[2]InoueY,YokoyamaT,YamasakiN,etal.Nature,1989,341(6239),225—226[3]InoueY,YokoyamaT,YamasakiN,etal.J.Am.Chem.Soc.,1989,111,6480[4]InoueY,YamasakiN,YokoyamaT,etal.J.Org.Chem.,1992,571332—1345[5]InoueY,MatsushimaE,WadaT.J.Am.Chem.Soc.,1998,12010687—10696[6]InoueY,IkedaH,KanedaM,etal.J.Am.Chem.Soc.,2000,122,406—407[7]InoueY,NakagawaK,TongLH,etal.J.Photochem.Photobiol.,AChem.,1993,7161—64[8]童林荟(TongLH),井上佳久(InoueY).全国第八届大环化学学术讨论会(8thNationalAcademicSymposiumonMacrocyclicChemistry),论文集(BookAbstrctofAcademicThesis).郑州大学出版社(ZhengzhouUniversityPress),1996.37[9]侯智杰(HouZJ).中国科学院兰州化学物理研究所硕士学位论文(MasteralThesisofLanzhouInstituteofChemicalPhysics,ChineseAcademyofSciences).1992[10]TongLH,HouZJ,InoueY,etal.J.Chem.Soc.,PerkinTrans.,1992,1253—1257[11]井上佳久(InoueY),侯智杰(HouZJ),童林荟(TongLH)等.第11回环糊精讨论会(11thNationalSymposiumonCyclodextrins),会议论文集(CollectionofAcademicThesis),Japan,1992.B08[12]鲁润华(LuRH),杨敏(YangM),曹玉娟(CaoYJ).(unpublishedresults)[13]井上佳久(InoueY),侯智杰(HouZJ),童林荟(TongLH)等.第12回环糊精讨论会(12thNationalSymposiumonCyclodextrins),会议论文集(CollectionofAcademicThesis).Japan,1993.B123,B1124[14]GaoXM,TongLH,InoueY,etal.Synth.Commun.,1995,25703—710[15]童林荟(TongLH),高兴明(GaoXM).全国第七届大环化学学术讨论会,(7thNationalAcademicSymposiumonMaclocyclicChemistry)论文集(BookAbstractofAcademicThesis).济南(Jinan)山东大学出版社(ShandonUniversityPress),1994.140—143[16]GaoXM,ZhangYL,TongLH,etal.J.InclusionPhenomenaandMacrocyclicChemistry,2001,3977—80[17]HaoAY,TongLH,ZhangFS,etal.CarbohydrateResearch,1995,277333—337[18]HaoAY,TongLH,ZhangFS.ChineseChemicalLetters,1994,5(8)645—646[19]KajtarM,Harvath2ToroC,KuthiE,SzejtliJ.ActaChim.Acad.Sci.Hung.,1982,110327[20]TongLH.FinalReportofInouePhotochirogenesisProject,ERATO,JSTS,LanzhouInstituteofChemicalPhysics,ChineseAcademyofScience,2001,813[21]童林荟(TongLH).环糊精化学基础与应用(CyclodextrinChemistryFoundationandApplication).北京(Beijing)科学出版社(SciencePress),2001.144[22]InoueY,TongLH,WuHM,etal.J.Chem.Soc.,PerkinTrans.2,1998,1807—1816[23]InoueY,WadaT,TongLH,etal.J.Org.Chem.,2000,658041—8050[24]YamamotoK,TongLH,InoueY.(unpublishedresult)[25]InoueY,DongF,Yamamotok,etal.J.Am.Chem.Soc.,1995,11711033—11034[26]WadaT,I