In the course of exploring the chemistry of thiapen6 as a means for synthesizing novel solid- state materials, we discovered a new and versatile procedure for constructing the tetrathiafulvalene skeleton that does not require coupling of molecular half-units. The synthesis outlined in Scheme I uses thiapendione (2) 6 as the starting point. Selective reaction of one of the carbonyl centers of 2 was affected by using a phase-transfer reagent ...