The synthesis of a number pyrrolo-annelated tetrathiafulvalenes, including the parent bis (pyrrolo [3, 4-d]) tetrathiafulvalene (7) is decribed. Starting from readily available 4, 5-bis (bromomethyl)-1, 3-dithiole-2-thione (14) and sodium tosylamide, the parent 7 and the asymmetric monopyrrolo tetrathiafulvalenes 23a, b were prepared in good yields via a nonclassical and simple pyrrole synthesis. Furthermore, a series of asymmetrical N- ...