定义Definition
对映异构体是互为镜像、但不能重合的一对立体异构体。只有手性分子才有对映异构体;最常见的情况是分子含一个连有四个不同基团的碳原子。
Enantiomers are a pair of stereoisomers that are mirror images of each other but cannot be superimposed. Only chiral molecules have enantiomers; the commonest case is a molecule with one carbon atom bonded to four different groups.
性质Properties
一对对映体的熔点、沸点、密度、溶解度和与非手性试剂的反应完全相同。不同之处在于:它们使平面偏振光旋转的角度相等、方向相反,分别称为右旋(+)和左旋(−);与其他手性物质(如酶、受体)作用时可能差别很大。等量对映体的混合物称为外消旋体,不旋光。
Enantiomers have identical melting and boiling points, density, solubility and reactions with achiral reagents. They differ in rotating plane-polarised light by equal angles in opposite directions, dextrorotatory (+) and laevorotatory (−), and they may behave very differently towards other chiral substances such as enzymes and receptors. An equal mixture is a racemate and shows no optical rotation.
表示与命名Drawing and naming
用楔形键和虚楔键表示手性碳上基团的空间取向,画出镜像即得另一对映体。每个手性中心的构型用 CIP 规则标为 R 或 S;旋光方向(+/−)需由实验测定,与 R/S 没有固定对应关系。
Wedged and hashed bonds show the arrangement of groups at a chiral carbon; drawing the mirror image gives the other enantiomer. Each centre is labelled R or S by the CIP rules; the sign of rotation (+/−) must be measured and has no fixed link to R/S.
意义Significance
生物体内的氨基酸几乎都是 L 型,糖多为 D 型,许多药物只有一种对映体有效。由非手性原料合成手性分子通常得到外消旋体,需拆分或采用不对称合成。
Amino acids in living things are almost all L and sugars mostly D, and many drugs work as only one enantiomer. Making a chiral molecule from achiral starting materials usually gives a racemate, which must be resolved, or asymmetric synthesis is used.
年表Timeline
- 1848
巴斯德用镊子分开酒石酸盐的左右手晶体
Pasteur separates left- and right-handed tartrate crystals with tweezers
- 1874
范特霍夫与勒贝尔用四面体碳解释对映异构
van 't Hoff and Le Bel explain enantiomers with the tetrahedral carbon
- 2001
诺尔斯、野依良治、夏普莱斯因不对称催化获诺贝尔化学奖
Knowles, Noyori and Sharpless receive the Nobel Prize in Chemistry for asymmetric catalysis