厦门大学化学化工学院：《有机化学》课程教学资源（课件讲稿，双语版）第五章 立体化学：手性分子（5.14-5.17）Relating Configurations Through Reactions

ORGANIC CHEMISTRY Chapter 5 5.14 Relating Configurations Through Reactions in Which No Bonds to the stereocenter are Broken 通过未涉及立体中心断键反应相对应的构型 Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 5 5.14 Relating Configurations Through Reactions in Which No Bonds to the Stereocenter are Broken 通过未涉及立体中心断键反应相对应的构型

ORGANIC CHEMISTRY Chapter 5 CH3 CH H-1CH2-OH +H-Cl △ H--CH2-CI+H-OH HOcH CHCH (S)-2-Methy l-1-butano (S)-1-Chloro-2-methylbutane laid 5.756 b=+1.64 CHb-Br CHo-H Zn /h(ZnBr2) H OH H OH retention od configuration CH,CH CHCH (R)-1-Bromo-2-butanol (S)-2-Butanol Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 5 CH3 H CH2 CH2CH3 OH + H Cl ∆ CH3 H CH2 CH2CH3 Cl + H OH (S)-2-Methyl-1-butanol (S)-1-Chloro-2-methylbutane [α]D25 = −5.756 [α]D25 = +1.64 CH2 H OH CH2CH3 Br CH2 H OH CH2CH3 H Zn / H+ (−ZnBr2) retention od configuration (R)-1-Bromo-2-butanol (S)-2-Butanol

ORGANIC CHEMISTRY Chapter 5 5.14 Relative and Absolute Configurations 相对构型与绝对构型 Before 1951 only relative configurations of chiral molecules were known g Configurations of chiral molecules were related to each other through reactions of known stereochemistry o The standard compound was glyceraldehyde CHO CHO H-OH HO-H ChOH Glyceraldehyde CHOH D-(+)-Glyceraldehyde L-()-Glyceraldehyde D-(+)-甘油醛 L()-甘油醛 Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 5 5.14A Relative and Absolute Configurations 相对构型与绝对构型 Before 1951 only relative configurations of chiral molecules were known. Configurations of chiral molecules were related to each other through reactions of known stereochemistry. The standard compound was glyceraldehyde. CHO H OH CH2OH CHO HO H Glyceraldehyde CH2OH D-(+)-Glyceraldehyde D-(+)-甘油醛 L-(–)-Glyceraldehyde L-(–)-甘油醛

ORGANIC CHEMISTRY Chapter 5 CHO COoH CO,H Hgo H OH H OH— H OH [O] CHoO CH,OH CH D-(+)-Glyceraldehyde D-()-Glyceric acid D-()-Lactic acid D-(+)-甘油醛 D-(-)-甘油酸 D-(-)-乳酸 H CHOH的久 CHO CH OH OH H OH CH,OH O] CO,H D-form D-form D-form Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 5 CHO H OH CH2OH D-(+)-甘油醛 CO2H H OH CH2OH D-(−)-甘油酸 CO2H H OH CH3 D-(−)-乳酸 HgO [O] [H] D-(+)-Glyceraldehyde D-(−)-Glyceric acid D-(−)-Lactic acid CHO H OH CH2OH CH3 H OH CH2OH CH3 H OH CO2H D-form D-form D-form [H] [O] ???

ORGANIC CHEMISTRY Chapter 5 o The spatial arrangement of substituents at a chirality center is its absolute configuration o In 1951 Bijvoet using a special technique of X-ray diffraction was able to show conclusively that(+)- tartaric acid had the absolute configuration show below COH H-OH Ho-H CO2 QH L-fo (+)-Tartaric acid Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 5 The spatial arrangement of substituents at a chirality center is its absolute configuration. In 1951 Bijvoet using a special technique of X-ray diffraction was able to show conclusively that (+)- tartaric acid had the absolute configuration show below. CO2H H OH HO H CO2H (+)-Tartaric acid L-form

ORGANIC CHEMISTRY Chapter 5 5.15 Separation of Enantiomers Resolution 对映异构体的分离:拆分 Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 5 5.15 Separation of Enantiomers: Resolution 对映异构体的分离：拆分

ORGANIC CHEMISTRY Chapter 5 5. 15A Pasteur's Method for Separating Enantiomers Not generally applicable to the separation of enantiomers Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 5 5.15A Pasteur’s Method for Separating Enantiomers Not generally applicable to the separation of enantiomers

ORGANIC CHEMISTRY Chapter 5 5. 15B Current method for resolution of Enantiomers Method 1 Racemic a single enantiomer a mixture of form of other compound diastereomers Se ted (+)-form eparate form Method 1 Resolution by enzymes Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 5 5.15B Current Method for Resolution of Enantiomers Method 1 a mixture of diastereomers a single enantiomer of other compound Racemic form + (+)-form (+)-form Separated (–)-form (–)-form Method 1 Resolution by enzymes

ORGANIC CHEMISTRY Chapter 5 (+)RCOH (-R'Nh2 (+)-RCO2(-RoNI +非对映 +(-)-RCO2(-)-RNH3 (+-RcO2()-RNH3 分级结晶 (-)-RCO2(-)-RNH3 HC (+)-rCo2H+(-rNH HCI ()-RCO2H+(-RNH3 Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 5 (+)-RCO2H + (-)-RCO2−(-)-R'NH3 非对映 HCl HCl (+)-RCO2H + (-)-R'NH3 (-)-RCO2H + (-)-R'NH3 (+)-RCO2−(-)-R'NH3 分级结晶 (-)-R'NH2 (+)-RCO2−(-)-R'NH3 (-)-RCO2−(-)-R'NH3

ORGANIC CHEMISTRY Chapter 5 OH 马钱子碱 OH 0()(按酸性对映体的方法拆分) Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY Department of Chemistry, Xiamen University Chapter 5 OH * (+) O O O + O O O OH * (+) 马钱子碱 (按酸性对映体的方法拆分)