New Tetrathiafulvalenes for Advanced Materials

Highly Functionalized Tetrathiafulvalenes: Riding along the Synthetic Trail from Electrophilic Alkynes

“…Subsequent Diels−Alder cycloaddition with oligo(1,3-dithiole-2,4,5-trithione) 29,76,77 followed by cross-coupling with 4,5-bis(methoxycarbonyl)-2-oxo-1,3-dithiole produced precursor 141 . Unfortunately, although compound 141 underwent loss of cyclopentadiene in the oxidative step in cyclic voltammetry, preparative synthesis of the corresponding TTF 131 has been so far unsuccessful (Scheme a) . After this work, a reverse synthetic strategy has been used by Zhang et al, who synthesized the TTF-dithiin-quinone framework and subjected it to bis-olefination with the anion phosphonate P .…”

“…Unfortunately, although compound 141 underwent loss of cyclopentadiene in the oxidative step in cyclic voltammetry, preparative synthesis of the corresponding TTF 131 has been so far unsuccessful (Scheme 70a). 202 After this work, a reverse synthetic strategy has been used by Zhang et al, who synthesized the TTF-dithiin-quinone framework and subjected it to bis-olefination with the anion phosphonate P. Similarly to 141, the intermediate 141′ did not undergo the retro Diels-Alder reaction, which would have provided compound 131′ (Scheme 70b). 203 A straightforward synthesis of the new π-donor 130 which shows the typical H-shape design which promises to improve the properties of highly extended and sulfur-rich T-shape compounds was reported.…”