enantiotopism

Enantiotopism refers to a specific type of stereoisomerism in molecules where two atoms or groups within a molecule are enantiotopic if they are identical by symmetry but would produce enantiomers if one were replaced by a different atom or group. This concept is particularly relevant in the context of stereochemistry and reaction mechanisms.

Enantiotopic atoms or groups are not stereocenters themselves, meaning their replacement does not directly create a chiral center. However, their environment within the molecule is chiral. This chirality arises from the overall asymmetry of the molecule. A common way to identify enantiotopic atoms or groups is to consider replacing one of them with a hypothetical atom or group, say 'X', and then checking if the resulting molecule is chiral. If it is, and if replacing the other identical atom or group with 'X' yields the enantiomer of the first product, then the original atoms or groups were enantiotopic.

For example, in a molecule like propanal (CH3CH2CHO), the two hydrogen atoms on the alpha-carbon (the carbon adjacent to the carbonyl group) are enantiotopic. If one of these hydrogens were replaced by a deuterium atom, the resulting molecule would be chiral. Replacing the other alpha-hydrogen with deuterium would yield the enantiomer of this product.

Enantiotopic relationships are crucial when considering reactions that occur at these positions, such as enzymatic reactions or reactions with chiral reagents. These reactions can distinguish between enantiotopic atoms or groups, leading to the selective formation of one enantiomer over the other. This selectivity is a cornerstone of asymmetric synthesis.