6 对映异构体的拆分.pptVIP

A collection containing equal amounts of the two enantiomeric forms of a chiral molecule is called a: racemic mixture or racemate.;Molecules with 2 or more chiral centers have more isomers.;A mixture containing predominantly one enantiomer is termed as: Enantiomerically Enriched, or Enantioenriched.;Quantitating Enantiopurity (对映纯度） Enantiomeric Excess (%e.e.) : Enantiopurity is usually reported in terms of “enantiomeric excess” ;Most of chiral compounds are unavailable in enantioenriched form ;Methods for obtaining enantioenriched compounds 1. Directly from chiral pool(手性源) 2. Synthesis from enantioenriched chiral pool starting products. 3. Synthesis using enantioenriched chiral pool auxiliaries(辅助物). 4. Enantioselective catalysts(催化剂). 5. Classical resolution chromatographic enantioseparation (对映性分离）. 6. Spontaneous(自发的)resolution.;Classical Resolution Enantiomers have identical physical properties, and consequently cannot be directly separated by conventional methods such as distillation(蒸馏), crystallization, sizing(定量), or chromatography on conventional stationary phases. Physical separation of the enantiomers comprising a racemic mixture requires the use of some external enantiopure, enantioenriched material, or device.;对映体具有相同的物理性质(如熔点，沸点，溶解度，折射率，酸性，密度等)，热力学性质(如自由能，焓、熵等)和化学性质。除非在手性环境(如手性试剂，手性溶剂)中才表现出差异。对映体对偏振光的作用不同，它们的比旋光度数值相同，但方向相反。对映体的生物活性不相同，化学反应中表现出等速率。;Classically, enantiomers have been separated by forming diastereomeric salts or derivatives with enantioenriched chiral pool reagents. Since these diastereomeric derivatives are no longer enantiomers. They (diastereomeric derivatives) can be separated by conventional separation methods such as crystallization, or chromatography on silica or other conventional stationary phases.;Method of resolution （拆分） ; 羧基＋光学活性碱 碱基＋光学活性酸 差向异构体：不同的物化性质。 差向异构体盐：不同的结晶特性，适合的溶剂中可进行分步结晶。 缺点：常不能够经一步结晶达到完全分离； 长时间的分离过程。;差向异构体盐;天然存在的生物碱：好的光学活性碱试剂，如brucine， ephedrine，strych