Chemoselectivity

Chemical reactions are defined usually in small contexts (only up to a small number of neighbouring atoms), such generalizations are a matter of utility. The preferential outcome of one instance of a generalized reaction over a set of other plausible reactions, is defined as chemoselectivity. ^[1]

In another definition, chemoselectivity refers to the selective reactivity of one functional group in the presence of others; often this process in convoluted and protecting groups are used to ensure that this outcome can be attained. Practicing chemists typically try to predict whether or not an instance of a particular generalized reaction will yield product based on the molecular connectivity alone. Such predictions based on connectivity are generally considered plausible, but the physical outcome of the actual reaction is ultimately dependent on a number of factors that are practically impossible to predict to any useful accuracy (solvent, atomic orbitals, etc.).

As such, chemoselectivity can be difficult to predict, but observing selective outcomes in cases where many reactions are plausible, is common. Examples include the selective organic reduction of 4-nitro-2-chlorobenzonitrile to the corresponding aniline, 4-amino-2-chlorobenzonitrile and the greater relative chemoselectivity of sodium borohydride reduction vs. lithium aluminium hydride reduction. In another example, the compound 4-methoxyacetophenone is oxidized by bleach at the ketone group at high pH (forming the carboxylic acid) and oxidized by EAS (to the aryl chloride) at low pH ^[2]

References

1. ^ IUPAC Gold Book definition for chemoselectivity.
2. ^ Ballard, C. E. (2010). "pH-Controlled Oxidation of an Aromatic Ketone: Structural Elucidation of the Products of Two Green Chemical Reactions". Journal of Chemical Education 87 (2): 190–193. Bibcode 2010JChEd..87..190B. doi:10.1021/ed800054s.  edit