Abstract–The preparation of oxazole-2 (3H)-thiones (OXTs) by condensation of thiocyanic acid on α-hydroxycarbonyl substrates has been revisited. Extension to more complex scaffolds afforded chiral OXTs, whereas carbohydrate-fused 2-alkylsulfanyl-1, 3-oxazolines led to original hemiaminal structures. A survey of the reactivity of OXTs with various electrophiles showed S-or N-chemoselectivity based on HSAB parameters. Antimicrobial ...