(±)-Aerothionin,(±)-homoaerothionin, and (±)-aerophobin-1 have been successfully synthesized using phenolic oxidation of the methyl pyruvate oxime derivative with thallium (III) trifluoroacetate as a key step. The stereostructure of aerophobin-2 has been also established by comparison of the 1 H NMR spectrum with those of related compounds.