|
Enantioselective synthesis, also called chiral synthesis or asymmetric synthesis, is defined by IUPAC as: a chemical reaction (or reaction sequence) in which one or more new elements of chirality are formed in a substrate molecule and which produces the stereoisomeric (enantiomeric or diastereoisomeric) products in unequal amounts. Put more simply: it is the synthesis of a compound by a method that favors the formation of a specific enantiomer or diastereomer. Enantioselective synthesis is a key process in modern chemistry and is particularly important in the field of pharmaceuticals, as the different enantiomers or diastereomers of a molecule often have different biological activity. ==Overview== Many of the building blocks of biological systems, such as sugars and amino acids, are produced exclusively as one enantiomer. As a result of this living systems possess a high degree of chemical chirality and will often react differently with the various enantiomers of a given compound. Examples of this selectivity include: * Flavour: the artificial sweetener aspartame has two enantiomers. L-aspartame tastes sweet, yet D-aspartame is tasteless * Odor: ''R''-(–)-carvone smells like spearmint yet ''S''-(+)-carvone, smells like caraway. * Drug effectiveness: the antidepressant drug Citalopram is sold as a racemic mixture. However, studies have shown that only the (''S'')-(+) enantiomer is responsible for the drug's beneficial effects. * Drug safety: ''D''‑penicillamine is used in chelation therapy and for the treatment of rheumatoid arthritis. However ''L''‑penicillamine is toxic as it inhibits the action of pyridoxine, an essential B vitamin. As such enantioselective synthesis is of great importance; but it can also be difficult to achieve. Enantiomers possess identical enthalpies and entropies, and hence should be produced in equal amounts by an undirected process - leading to a racemic mixture. The solution is to introduce a chiral feature which will promote the formation of one enantiomer over another via interactions at the transition state. This is known as asymmetric induction and can involve chiral features in the substrate, reagent, catalyst or environment and works by making the activation energy required to form one enantiomer lower than that of the opposing enantiomer.〔Page 1226〕 Asymmetric induction can occur intramolecularly when given a chiral starting material. This behaviour can be exploited, especially when the goal is to make several consecutive chiral centres to give a specific enantiomer of a specific diastereomer. An aldol reaction, for example, is inherently diastereoselective; if the aldehyde is enantiopure, the resulting aldol adduct is diastereomerically and enantiomerically pure. 抄文引用元・出典: フリー百科事典『 ウィキペディア(Wikipedia)』 ■ウィキペディアで「Enantioselective synthesis」の詳細全文を読む スポンサード リンク
|