郑州大学有机化学4立体化学.pptVIP

(R)-(-)-肾上腺素 (S)-(+)-肾上腺素 左旋异构体活性比右旋异构体强约27倍 碳正离子中间体 经烯醇化发生外消旋化 13. Chiral synthesis (手性合成) Optically inactive reactants yield optically inactive products. Asymmetric synthesis, also called chiral synthesis, enantioselective synthesis or stereoselective synthesis, is organic synthesis that produces a preponderance of one enantiomer over its mirror image. 一个分子在对称环境下反应, 不可能有选择性。（左旋体与右旋体过渡态能量相同、反应活化能相同，反应速率相同) 。 *1.手性反应物 *2.手性试剂 *3.手性溶剂 *4.手性催化剂 *5.在反应物中引入手性 不对称合成常采用的方法 非手性分子 有一个手性中心 外消旋体 产物有二个手性中心，非对映体 反应物有一个手性中心 （多） （少） K. Barry Sharpless The Nobel Prize in Chemistry 2001 Sumarry Basic concepts Determining chirality of molecules Assigning atomic configurations (R-/S-) Fischer projection * * 4.4 Some concepts (几个概念) Enantiomeric Excess (对映体过量) (ee) Where M+ is the mole fraction of the dextrorotatory enantiomer, and M- the mole fraction of the levorotatory one. Optical purity (光学纯度) (op) 已知2-甲基-1-氯丁烷的[α] = +1.64°，现有一个不对称合成该化合物的样 品，经测定其比旋光度为+0.82°，求该样品的光学纯度百分率和 (+)、(-) 对映体的组成比。 右旋体∶左旋体 = 75∶25 Prochiral carbon (潜手性碳) If two identical substituents are attached to a sp3-hybridized atom, the descriptors pro-R and pro-S are used to distinguish between the two. Promoting the pro-R substituent to higher priority than the other identical substituent results in an R chirality center at the original sp3-hybridized atom, and analogously for the pro-S substituent. If a symmetric carbon can be substituted and becomes asymmetric in a single step, it is called a ‘prochiral carbon’. A trigonal planar sp2-hybridized atom can be converted to a chiral center when a substituent is added to the re or si face of the molecule. A face is labeled re if, when looking at that face, the substituents at the trigonal atom are arranged in decreasing Cahn-Ingold-Prelog priority order in a clockwise order, and si if the priorities decrease in counter-clockwise order. re/si face 5. Molecules with two different chiral carbons (含两个不同手性碳的分子) Ⅳ Ⅰ Ⅱ Ⅲ (2S, 3S)-~ (2R, 3R)-~ (2R, 3S)-~ (2S