Named after Dalziel Hammick | Reaction type Coupling reaction | |
The Hammick reaction, named after Dalziel Hammick, is a chemical reaction in which the thermal decarboxylation of α-picolinic (or related) acids in the presence of carbonyl compounds forms 2-pyridyl-carbinols.
Using p-cymene as solvent has been shown to increase yields.
Reaction mechanism
Upon heating α-picolinic acid will spontaneously decarboxylate forming the so-called 'Hammick Intermediate' (2), which can be viewed as an aromatic ylide. In the presence of a strong electrophile, such as an aldehyde or ketone, this species will undergo nucleophilic attack faster than protonation. After nucleophilic attack intramolecular proton transfer yields the desired carbinol (4).
The scope of the reaction is effectively limited to decarboxylating acids where the carboxyl group is α to the nitrogen, (reactivity has been reported when the acids are located elsewhere on the molecule but with low yields) thus suitable substrates are limited to the derivatives of α-picolinic acid including the α-carboxylic acids of quinoline and isoquinoline.