Stereospecificity - Examples

Examples

Nucleophilic substitution at sp3 centres can proceed by the stereospecific S_N2 mechanism, causing only inversion, or by the non-specific S_N1 mechanism, the outcome of which can show a modest selectivity for inversion, depending on the reactants and the reaction conditions to which the mechanism does not refer. The choice of mechanism adopted by a particular reactant combination depends on other factors (steric access to the reaction centre in the substrate, nucleophile, solvent, temperature).

For example, tertiary centres react almost exclusively by the S_N1 mechanism whereas primary centres (except neopentyl centres) react almost exclusively by the S_N2 mechanism. When a nucleophilic substitution results in incomplete inversion, it is because of a competition between the two mechanisms, as often occurs at secondary centres, or because of double inversion (as when iodide is the nucleophile).

The addition of singlet carbenes to alkenes is stereospecific in that the geometry of the alkene is preserved in the product. For example, dibromocarbene and cis-2-butene yield cis-2,3-dimethyl-1,1-dibromocyclopropane, whereas the trans isomer exclusively yields the trans cyclopropane.

This addition remains stereospecific even if the starting alkene is not isomerically pure, as the products' stereochemistry will match the reactants'.

The disrotatory ring closing reaction of conjugated trienes is stereospecific in that isomeric reactants will give isomeric products. For example, trans,cis,trans-2,4,6-octatriene gives cis-dimethylcyclohexadiene, whereas the trans,cis,cis reactant isomer gives the trans product and the trans,trans,trans reactant isomer does not react in this manner.