We report improved protocols for the synthesis of thiazolium precatalysts from primary amines, carbon disulfide, and α-halo ketones. For N-alkyl-substituted derivatives, yields of the corresponding thiazolethiones can be dramatically improved by isolating the intermediate dithiocarbamates. In most cases, meta-chloroperbenzoic acid can advantageously replace H2O2 in acetic acid for the oxidation of thiazolethiones into thiazoliums. This approach was applied to the synthesis of a thiazolium featuring a 2-adamantyl N-substituent, the corresponding persistent carbene, and its dimer.