Stereoselectivity

In chemistry, stereoselectivity is the property of a chemical reaction in which a single reactant forms an unequal mixture of stereoisomers during the non-stereospecific creation of a new stereocenter or during the non-stereospecific transformation of a pre-existing one. The selectivity arises from differences in steric effects and electronic effects in the mechanistic pathways leading to the different products. Stereoselectivity can vary in degree but it can never be total since the activation energy difference between the two pathways is finite. However, in favorable cases, the minor stereoisomer may not be detectable by the analytic methods used.

An enantioselective reaction is one in which one enantiomer is formed in preference to the other, in a reaction that creates an optically active product from an achiral starting material, using either a chiral catalyst, an enzyme or a chiral reagent. The degree of selectivity is measured by the enantiomeric excess. An important variant is kinetic resolution, in which a pre-existing chiral center undergoes reaction with a chiral catalyst, an enzyme or a chiral reagent such that one enantiomer reacts faster than the other and leaves behind the less reactive enantiomer, or in which a pre-existing chiral center influences the reactivity of a reaction center elsewhere in the same molecule.

A diastereoselective reaction is one in which one diastereomer is formed in preference to another (or in which a subset of all possible diastereomers dominates the product mixture), establishing a preferred relative stereochemistry. In this case, either two or more chiral centers are formed at once such that one relative stereochemistry is favored, or a pre-existing chiral center (which needs not be optically pure) biases the stereochemical outcome during the creation of another. The degree of relative selectivity is measured by the diastereomeric excess.

Stereoconvergence can be considered an opposite of stereoselectivity, when the reaction of two different stereoisomers yield a single product stereoisomer.

The quality of stereoselectivity is concerned solely with the products, and their stereochemistry. Of a number of possible stereoisomeric products, the reaction selects one or two to be formed.

Read more about Stereoselectivity:  Examples, Stereoselective Biosynthesis

Other articles related to "stereoselectivity":

Kumada Coupling - Selectivity - Stereoselectivity
... Conversely, a Kumada coupling using vinylic Grignard reagents proceeds without stereospecificity to form a mixture of cis- and trans-alkenes ... The degree of isomerization is dependent on a variety of factors including reagent ratios and the identity of the halide group ...
Meerwein–Ponndorf–Verley Reduction - Stereoselectivity
... One method of achieving the asymmetric MPV reduction is with the use of chiral hydride donating alcohols ... The use of chiral alcohol (R)-(+)-sec-o-bromophen-ethyl alcohol gave 82%ee (percent enantiomeric excess) in the reduction of 2-chloroacetophenone ...