高等有机化学-结构与光学活性1

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1、AdvancedOrganicChemistry(1)高等有机化学（I）Instructor:JingKuiYANG杨镜奎CollegeofChemistryandChemicalEngineeringGraduateUniversityofCAS(GUCAS)Chem_homework1@126.comhttp://chem.gucas.ac.cn/jkyang/courses.htm1问题解答:二等份型与酮的构象21-Butene•Eclipsed(重叠)morestablethanbisected(二等分型)andCismorestablethandby0.15Kcal/molIncre

2、asingsizeofgroupcanmakethebisectedmorestable(基团大二等分型稳定性增)3CramPrinciple1一般适用于以下试剂:MeMgI,NaBH4,LiAlH44CramPrinciple2IfH-BondformedbetweentheC=Oandtheasymmetricα–Carbon,thereagentwillattackthethelessstericsideoftheringcontainingtheH-Bond(从含氢键环的空间阻碍小的一边进攻碳原子）。5CornforthPrinciple:ifaCl,Br,IorFatomexiste

3、dattheasymmetricα–CarbonoftheC=O,itwilltaketherepulsiveconformationwiththeC=O,butreagentstillattackitforthelessstericside(卤素远离羰基，小阻碍方向进攻）6Chapt3Stereochemistry(立体化学)Introduction:HistoryandOpticity(旋光)Conformation(构象)Chiralmolecules(手性分子)andEnantiomers(对映异构体)Configuration(构型)Constitutional(结构:链,位置,官能

4、团)&Stereoisomers(立体)Isomers(顺反,对映,构象:消旋)Structure&OpticalActivity(结构与光学活性)Stereochem.andOrgSynthesis(立体化学与合成)ApplicationofSpectrainStereochem.(光谱:NMR,IR,UV,ORD/CD在立体化学中的应用)Isolationofisomers(异构体的分离)7TartaricAcid酒石酸ChiralCheiros(Hand)8Chapt3.3Chirality(手性)/Configuration(构型)/Enantiomers对映异构体Chirality

5、Cis-TransIsomerism(顺反异构)Enantiotropy(对映异构)andD/L,R/SNomenclature(命名)DifferenceBetweenConfiguration&ConformationTheDeterminationofachiral(Configuration)Propertiesofenantiomers9ChiralityChiralcarbon(asymmetriccarbonatom):4differentsubstitutesattached(stereoorstructures)tooneCarbonatoms一个碳原子与4个不同基团连接(结

6、构或立体不同)10Dissymmetric(非对称性)Molecule:分子与镜像不重叠为旋光性的必要条件Dissymmetric有旋光性Symmetric(对称)无旋光性11Symmetricfactors:σ:平面对称因素i:中心对称因素Cn:旋转轴对称因素Sn:更迭旋转轴对称因素121314Achiralmolecules(非手性分子/对称分子)σ,I,SnAsymmerticmolecules(非对称分子)CnNonAsymmetricMolecule(不对称分子)noanyofσ,I,Sn,Cn(无任何对称性)手性分子15Cumulativedoublebond累积双键化合物顺/反C

7、is/TransR/S表示单数双键(单数双键)无旋光性可有旋光性16Ph>HHO>未共用电子对178isomersmoreTotalisomersare:24=16构型:1618Cyclobutane•Notplanar-reducedeclipsinginteractions构型变化构象变化19D、Lrelativeconfiguration(相对构型)D,LExpressionConfigur