Synthesis of 1,3-Dithiin Dithioortho Esters from the Reaction of Fischer Carbenes and 3H-1,2-Dithiole-3-thiones

Abstract

[reaction: see text] Tricyclic 4-ethyl-5-thioxo-3H,5H-bis[1,2]dithiolo[3,4-d][4,3-b]pyrrol-3-one and monocyclic 3H-1,2-dithiole-3-thione derivatives reacted with Fischer carbene complexes, giving 1,3-dithiin dithioortho esters through insertion of the carbenic carbon into the S-S bond next to the thiocarbonyl function of the substrate.

Alkynyl Fischer carbene complex as a traceless directing group for the regioselective cycloaddition of dithiolethiones to arylacetylene: synthesis of E-dithiafulvene thione and dithioesters

“…Similarly, reactions of 1b-e and 2 afforded, respectively, products 3b-e and 4b-e in variable yields (4e was not obtained). It is remarkable that we never obtained even traces of the product from the insertion of the carbene moiety into the S-S bond and some attempts of reacting 1a-b and 2 under the insertion conditions 12 (dioxane, 40 uC, 3 h) gave only traces of 3a-b in addition to a complex mixture of unstable products from which the insertion product could not be found. The reaction of the simple 5-methyl-1,2-dithiole-3-thione 1d and Fischer carbene 2 afforded, after aluminium oxide treatment, E-dithiafulvene thione 4d as orange crystals suitable for single crystal X-ray diffraction, which again confirmed the structure of 4d § as the E-isomer (Fig.…”

“…We have previously reported that 3H-1,2-dithiole-3-thione derivatives reacted with aryl Fischer carbene complexes, giving 1,3-dithiin dithioortho esters through insertion of the carbonic carbon into the S-S bond next to the thiocarbonyl function of the substrate. 12 In this communication we report the fully regioselective cycloaddition of dithiolethiones to alkynyl Fischer carbene complexes followed by stepwise elimination of methanol and chromium hexacarbonyl, which constitutes the first regioselective synthesis of E-dithiafulvene thiones and dithioesters.…”

Synthesis and Reactivity of 3H-1,2-dithiole-3-thiones

“…The formation of the trithiapentalene system was explained as a sequential process of reduction and substitution of fluorine atoms under the action of a sulfide anion followed by its addition and elimination of the vinyl sulfur atom, while the formation of the thiopyrane system was followed by a rearrangement of the trithiapentalene system. A number of 1,2-dithiole-3-thiones, both monocyclic and fused 11, were studied in the reaction with Fischer's carbene complex 96 [99]. Insertion of a carbene moiety into the S...S bond resulted in 1,3-dithiine-4-thiones 97 and 98, which were isolated after treatment of intermediate complexes 99 and 100 with methanol (Scheme 58).…”

“…Interestingly, in the first report on the reaction of 1,2-dithiole-3-thiones with Fischer carbene complexes, the authors argued that the incorporation of the carbene ligand occurs via the C3-C4 bond of the dithiole ring [100]. In a subsequent paper [99], an X-ray diffraction analysis of the compounds obtained was carried out and the initial data were corrected. The possibility of insertion of a carbon-containing particle was also demonstrated in the reaction of 1,2-dithiole-3-thione 102 with phosphonium ylides [101].…”

3H‐1,2‐Dithiole‐3‐thione derivatives as novel solvatochromic dyes

“…[40][41][42] These compounds have the characteristic of having a donor and acceptor group in the same molecule with an important contribution of structure 1 W and as a result they are reactive in front of electrophilic compounds. [43] Their UV-Vis spectrum shows well-defined absorption at $320 and $420 nm. We have shown that upon formation of an inclusion complex of 5-(1-butylthio)-3H-1,2-dithiole-3-thione (1a) (R 1 -Butyl, R 2 -H) with b-cyclodextrin the two absorption bands show a bathochromic and hipsochromic shift, respectively.…”