Synthesis of (Z)-Thiobutenynes Using NaOH or TBAOH As Activator: a Comparative Study

Organylthioenynes have became useful synthons recently, due their possible applications on the synthesis of enediynes and thiophenes. Recently the preparation of (Z)-thiobutenynes through hydrothiolation of 1,3-diacetylenes using NaBH4 and C4H9SSC4H9 to generate nucleophilic sulfur species such as BuS- and PhS- was reported by us. This systematic study allowed us to understand the limitations and potential of this methodology in the preparation of (Z)-thiobutenynes. However, (Z)- thiobutenyne 2, was obtained in low yield (40%) using this methodology.