The first general route to an unusual 5-membered thio-heterocyclic scaffold has been discovered utilizing readily available starting materials.With no conyenient synthesis, until now, we have developed a new route to a scaffold that has previously been incorporated into anti-HIV, chemopreventitive and anti-inflammatory drugs.The now readily available 5-membered thio-heterocycles can be synthesized as single enantiomers, tunable through thermodynamic or kinetic control.This allows predictable access to a number of different diastereomers through variation of reaction conditions.