Ketones are converted efficiently, in one step, to nitriles (R2CO -R2CHC=N) at temperatures between 0 and 45 O C by the use of TosMIC (tosylmethyl isocyanide) and base. This conversion is effectively a reductive cyanation, unlike the classical cyanohydrin reaction. The reaction is shown to be generally applicable.Tosylmethyl isocyanide (TosMIC, 1) is a synthon with diverse and steadily expanding applications. Thus far emphasis in the chemistry of TosMIC has centered mainly on heterocyclic synthesis. The preceding paper in this series deals with the synthesis of imidazoles from TosMIC and aldimines,2a and summarizes other azole (and azoline) syntheses.2 The present paper will show, however, that the application of TosMIC by no means is restricted to the domain of heterocyclic synthesis only.We here wish to concentrate on the use of TosMIC in an efficient, direct conversion of ketones to nitriles3 2

Tosylmethylisocyanid (I) reagiert mit den Oxo‐Verbindungen (II) in Gegenwart von Thalliumäthylat zu den 4‐Äthoxy‐oxazolinen (III), die sauer zu α‐Hydroxy‐aldehyden (IV) verseift werden können.