清华李艳梅5立体化学.ppt

共四个异构体： R R S S R S R S 3 3 3 3 3C 为非不对称碳 均有旋光性 互为对映异构体 3C 为不对称碳 均无旋光性 为内消旋体 互为非对映异构体 假不对称碳 Optical Stereomer C3 is symmetric Not optical Meso C3 is asymmetric 5.5.1 Cyclopropane, cyclobutane, and cyclopentane 5.5.2 derivatives of Cyclohexane 5.5 Cyclic compound 关键：平面分析 构象分析 5.5.1 Cyclopropane, cyclobutane, and cyclopentane 1, Cyclopropane A σ σ A A A A A A Trans- Cis- A B B A A B B A Cis- Trans- A A A A A A 2, Cyclobutane 3, Cyclopentane Learn on your own 5.5.2 Derivatives of Cyclohexane 顺-1,2-二取代 平面分析： 构象分析： Rotation Conformation transition (i)’ (i)’ (i)’’ (i)’’’ Rotation Conformation transition (ii)aa (ii)ee (iii)ee Conformation transition (iii)aa (iv)’ (iv)’’ 结论：就环己烷而言，平面分析与构象分析的结论相同。 5.6.1 Allene type compounds 5.6.2 Diphenyl compounds 5.6.3 Spiro compounds 5.6.2 Compounds with stereocenters other than carbon 5.6 Other chiral molecules 5.6.1 Allene type compounds 如果任何一端或两端的碳原子上连有相同取代基，则分子中存在对称面，该分子无手性。 反之，则该分子有手性。 5.6.2 Diphenyl compounds If on 2,2’,6,6’ sites there are large groups which block the rotation of the benzene rings, the two phenol rings are not on the same plane. 5.6.3 Spiro compounds 5.6.2 Compounds with stereocenters other than carbon Also, molecules with N, S, Si, As show this property. 5.7.1 Measure of polarity (Learn on your own) 5.7.2 Reslution of racemic compounds 5.7.3 Enantiomer excess percentage 5.7.4 Configuration and bio-activities 5.7 Measure of polarity and reslution of racemic compounds 5.7.1 Measure of polarity (Learn on your own) [α]D25 = 100α/(cl) 5.7.2 Reslution of racemic compounds 1, Chemical methods 50% D-Acid 50% L-Acid 50% D-Acid 50% D-Acid-D-Base 50% L-Acid-D-Base 2, Enzymatic methods 50% D-Compound 50% L-compound Enzyme Enzyme Used up NR 3, Crystal seeds 4, Column chromatography 5.7.3 Enantiomer excess percentage %ee = [R] - [S] [R] + [S] %R - %S = If [R]=[S]=50 %ee=0% If [R]=100, [S]=0 %ee=100% Meso Pure chiral