The reactions of 2-lithiated indole and 1-methylindole with elemental sulfur have been studied, leading eg to a rational approach to pentathiepino [6, 7-b] indoles 5 and 10. Notable amounts of the previously known tetrathiocino [5, 6-b: 8, 7-b′] diindole 11 could be observed as a side reaction in the preparation of 10. Treatment of the anions of indoline-2- thiones 6 or 7 with sulfur also gave the pentathiepins 5 or 10, respectively. In addition, a ...