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Updated: Jan 11, 2026

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Assembly strategy for thieno[3,2-b]thiophenes via a disulfide intermediate derived from
1Postovsky Institute of Organic Synthesis, Ural Branch of the Russian Academy of Sciences, Ekaterinburg, 620137, Russia.
Abstract:
A versatile synthetic route to thieno[3,2-b]thiophenes was elaborated from dimethyl 3-nitrothiophene-2,5-dicarboxylate. Nucleophilic substitution of the nitro group with sulfur nucleophiles, including thioacetate or disulfide anions as well as thioacetamide, yielded bis(thiophen-3-yl)disulfide and sulfide derivatives. The disulfide served as a suitable precursor for the preparation of 3-alkylthio-substituted thiophene-2,5-dicarboxylates by its one-pot reduction-alkylation using NaBH4 in DMF followed by an alkylating agent. Base-promoted cyclization of electron-deficient 3-alkylthio derivatives furnished 2-aryl-, 2-aroyl-, and 2-cyano-substituted thieno[3,2-b]thiophenes, bearing a 3-hydroxy group. This protocol broadens access to functionalized thieno[3,2-b]thiophenes with potential applications in pharmaceutical and materials chemistry.
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