Highly functionalized tetrathiafulvalenes: riding along the synthetic trail from electrophilic alkynes.

This review describes the synthesis of 1,3- and 1,2-tetrachalcogenafulvalenes, the chemical transformation of substituents, reactions of the ring systems and the synthesis of polymers with 1,3-tetrathiafulvalene units in the backbone and in the side chain. For selected charge-transfer complexes of tetrachalcogenafulvalenes the relation between molecular structure and solid-state structure, respectively, and electric conductivity are discussed. Superconducting properties of some charge-transfer complexes with tetrachalcogenafulvalenes as donor are reported. Preparations of important starting compounds for the synthesis of tetrachalcogenafulvalenes (like 1,2- and 1,3-dithiole, 1,3-thiaselenole, and 1,3-diselenole derivatives) have been considered in this review. Selected properties (melting point, UV-VIS absorption data and oxidation potentials) of 1,2- and 1,3-tetrachalcogenafulvalenes are summarized in appropriate tables.

Synthesis, Reactions, and Selected Physico-Chemical Properties of 1,3-and 1,2-Tetrachalcogenafulvalenes

Ferrocenyl and pyridyl methylenepyrans as potential precursors of organometallic electron-rich extended bipyrans: Synthesis, characterization and crystal structure

New extended analogues of TTF via triethylphosphite-mediated reaction

High-level single-reference calculations reveal that trimethylphosphine-mediated reductive dimerization of properly substituted (eg, CF3) ketones proceeds via initial formation of an oxaphosphirane intermediate, with the oxygen atom occupying an equatorial position at phosphorus In the "oxirane route", this oxaphosphirane intermediate loses a trimethylphosphine oxide unit, thus behaving as a carbene transfer agent toward a second carbonyl molecule and giving rise to a carbonyl ylide that cyclizates to the corresponding oxirane This in turn transfers the carbene unit to a second phosphine molecule, with loss of acetone, affording a phosphorane The latter undergoes typical Wittig reaction to the final homocoupling product through the oxaphosphetane intermediate The alternative direct conversion of oxaphosphirane into phosphorane constitutes the lowest energy path as it skips the highest barrier oxirane → phosphorane conversion The oxirane route is favored by the use of polar solvents and electron deficient carbonyl components The lowest barrier most exergonic process from oxaphosphirane is the pericyclic cycloaddition of the acetone C═O bond along the endocyclic P-C bond, furnishing the stable 1,3,2-dioxaphospholane product

T. Imakubo

Papers

A new synthetic route to TTF-vinylogues