Anchimeric-Assisted Spontaneous Hydrolysis of Cyanohydrins Under Ambient Conditions: Implications for Cyanide-Initiated Selective Transformations

Nitrile/cyanide hydrolysis is of importance from the perspective of organic chemistry, especially, prebiotic chemistry. Herein we report that cyanohydrins, generated by the reaction of cyanide with beta-keto acids and gamma-keto-alcohols, spontaneously hydrolyze under ambient conditions (aqueous medium, RT, and a range of pH). The spontaneous hydrolysis is affected by an intramolecular proton transfer and an intramolecular 5-exo-dig attack, but with a twist. In the case of beta-keto acids, the hydrolysis is mediated by the neighboring carboxylic acid group only at pH values less than 7, whereas in the case of gamma-keto-alcohols the hydrolysis is mediated by the neighboring hydroxyl group only at pH values greater than 7. The results, in combination with previous works, have implications for selective transformations of cyanide-initiated prebiotic systems chemistry.