Stereospecific Synthesis of 1,2-Difunctionalized Buta-1,3-Dienes via Tandem [3,3]–[3,3] Sigmatropic Rearrangements

Thermolysis of bis-thiocarbamates derived from but-3-yne-1,2-diols resulted in the formation of buta-1,3-dienes with carbamoylthio groups in positions 1 and 2 with good to excellent yields. The stereochemistry of the products is controlled by substituents at C-1 of the starting material and can be explained by chair-like reacting conformations.