Efficient synthetic methods for the construction of a wide variety of unsymmetrical tetrathiafulvalenes (TTFs) via the Me(3)Al-promoted reactions of organotin thiolates or selenolates with esters are described. Reaction of tin thiolates (3a-c and 10) and selenolates (3d, 5, and 7) with esters (11a,b) in the presence of Me(3)Al as a Lewis acid gave dihydrotetrathiafulvalene derivatives (12, 14, 15, and 17-20) and 1,3-dithiane derivatives (13 and 16). In addition, the synthesis of diselenadithiafulvalene derivatives (25-28) could be accomplished by Me(3)Al-mediated reaction of tin thiolate (2a) or selenolates (3d and 5) with esters (22a, 22d, and 24). Furthermore, the application of the Me(3)Al-promoted reaction of tin thiolate (34) with esters (11a-b, 22a-d, and 35a-b) for the synthesis of unsymmetrical TTFs-fused donors enabled us to obtain various TTFs-fused systems (29-33) in short steps.

The electrochemical properties of TTF(s)-DHTTF fused donors, the electrical conductivities of their radical-cation salts, and the crystal structure of (3)2Au12 are described.

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Radical-Cation Salts Based on TTF(s)-DHTTF (Dihydrotetrathiafulvalene) Fused Donors: Electrical Conductivities and Crystal Structure-(synthesis of the title compound (IIIa), electrochemical properties of the fused donors (III), electrical conductivities of therefrom derived radical-cation salts and crystal structure of (IIIc)). -(YAMADA, J.; MISHIMA, S.; ANZAI, H.; TAMURA, M.; NISHIO, Y.; KAJITA, K.; SATO, T.; NISHIKAWA, H.; IKEMOTO, I.; KIKUCHI, K.; Chem.

Synthesis of Unsymmetrical Tetrathiafulvalene Derivatives viaMe3Al-Promoted Reactions of Organotin Compounds with Esters. -It represents an efficient synthetic method for the preparation of a wide variety of unsymmetrical tetrathiafulvalenes and selenium analogues. -(YAMADA, J.; SATOKI, S.; MISHIMA, S; AKASHI, N.; TAKAHASHI, K.; MASUDA, N.; NISHIMOTO, Y.; TAKASAKI, S.; ANZAI, H.; J.