Palladium-catalyzed benzothieno[2,3-b]indole formation via dehydrative-dehydrogenative double C-H sulfuration using sulfur powder, indoles and cyclohexanonesElectronic supplementary information (ESI) available. CCDC 1030356. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4cc08370a

Palladium-catalyzed C-S bond formation via dehydrative-dehydrogenative double C-H sulfuration using sulfur powder is described. The dehydrogenated intermediates of cyclohexanones can be trapped to act as efficient aryl sources under an oxygen atmosphere. This procedure provides a novel approach for the preparation of benzothieno[2,3- b ]indoles. An efficient procedure for benzothieno[2,3- b ]indole formation via double C-H sulfuration using sulfur powder is described.