The unimolecular chemistry of the enol of ionized methyl glycolate: Formation of the hydrogen‐bridged radical cation [CH3O(H)…︁H…︁OCH].+

Abstract Dissociative ionization of methyl 2‐hydroxy‐isovalerate and dimethyl tartrate cleanly generate, via McLafferty rearrangements, the 1‐methoxy‐ethene‐1,2‐diol ion HOCHC(OH)OCH , 2. The unimolecular chemistry of 2, the enol form of ionized methyl glycolate, HOCH 2 C(O)OCH , 1, was investigated by a variety of tandem‐mass spectrometry‐based techniques using D‐ and 18 O‐labelled precursor molecules. The enol ion undergoes four major …