Jhong K. Kim

Thiosulfonium ions. Methylthiolation of 3-methylthio-1-butene and cis- and trans-1-methylthio-2-butene

Abstract Whereas sulfenyl reagents commonly add to carbon double bonds, addition to sulfur of 3-methylthio-1-butene precedes attack at carbon to give allylic thiosulfonium ions that form reversibly and which rearrange rapidly to trans -2-butenyl analogs. Likewise, rearrangement of cis - to trans -1-methylthio-2-butene occurs by way of thiosulfonium ions.

Intramolecular 1,6-hydride transfer in gaseous carbonium ions

The ion-molecule chemistry of 2-methoxyethanethiol reveals that the major product ion C3H7S+ is formed by way of an intramolecular hydride transfer in a precursor ion.

Gas-phase ionic reactions related to acid-catalysed carbonyl reactions in solution

Protonated esters, aldehydes, and ketones react with secondary and tertiary alcohols in the gas phase by way of nucleophilic displacement to eliminate water by alkyl–oxygen cleavage of the attacking alcohol, whereas alkoxycarbonium ions react with alcohols by an addition-elimination sequence.