Synthesis of Unsymmetrical Tetrathiafulvalene Derivatives via Me₃Al-Promoted Reactions of Organotin Compounds with Esters

Abstract

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.

13C NMR study of commensurate antiferromagnetism in (TMTTF)2Br

“…1(b)] was synthesized by coupling the dibutyltin complexes and was prepared as described. 18,19 The advantages of this method include the availability of 13 C-dichloroacetic acid methyl ester and the establishment of the precursors of butyltin and ester complexes. 18,20 One-sided 13 C-enriched TMTTF eliminates spectral splitting by Pake doublets and enables easy analysis of NMR spectra.…”

Correlation between non-Fermi-liquid behavior and antiferromagnetic fluctuations in (TMTSF)2PF6observed usingKimura1, Misawa2, Kawamoto3 2011Phys. Rev. B

“…Figure 2 shows one such candidate, the synthetic route of Yamada et al using dibutyltin complex. 15 Advantages of this method are that the isotope reagent dichloroacetic acid methyl ester is available and that Yamada et al have already established the precursors of 4 and 5. We synthesized single-site 13 C-enriched TMTSF by Yamada's method and characterized the products by mass spectroscopy and 1 H-NMR.…”

Tetrathiapentalene-based organic conductors

“…More than 80 types of BDT-TTP derivatives and selenium analogs have been synthesized by this method to date . Yamada et al developed another synthetic strategy for 5 (scheme 6) [42]. One of the TTF frameworks is constructed via the Me 3 Al-promoted reaction (Me = methyl) of organotin compound 9 prepared from 2 with ester 10 in this procedure.…”