A three-step synthetic approach to asymmetrically functionalized 4H-cyclopenta[2,1-b3,4-b′]dithiophenes

Sarah Van Mierloo, Peter J. Adriaensens, Wouter Maes, Laurence Lutsen, Thomas J. Cleij, Edith Botek, Benoît Champagne, Dirk J. Vanderzande

Research output: Contribution to journalArticle

Abstract

A convenient and efficient three-step route toward both symmetrically and asymmetrically functionalized 4H-cyclopenta[2,1-b:3,4-b′]dithiophenes has been developed. Using this method a broad collection of functionalized bridged bithiophenes can smoothly be accessed. Starting from 3-bromo-2,2′- bithiophene, prepared by Kumada coupling of 2-thienylmagnesium bromide with 2,3-dibromothiophene under Pd(dppf)Cl2 catalysis, lithiation and subsequent reaction with dialkyl ketones afforded (a)symmetrically dialkylated tertiary alcohol derivatives. By means of final Friedel-Crafts dehydration cyclization in sulfuric acid medium, these derivatives were converted to 4,4-dialkyl-4H-cyclopenta[2,1-b:3,4-b′]dithiophenes. Upon replacement of the dialkyl ketone reagent by ethyl levulinate, an ester-functionalized 4H-cyclopenta[2,1-b:3,4-b′]dithiophene was prepared, representing an attractive precursor for variously functionalized cyclopentadithiophene compounds.

Original languageEnglish
Pages (from-to)7202-7209
Number of pages8
JournalJournal of Organic Chemistry
Volume75
Issue number21
DOIs
Publication statusPublished - 5 Nov 2010

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Ketones
Derivatives
Cyclization
Bromides
Dehydration
Catalysis
Esters
Alcohols
ethyl levulinate
sulfuric acid

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Van Mierloo, S., Adriaensens, P. J., Maes, W., Lutsen, L., Cleij, T. J., Botek, E., ... Vanderzande, D. J. (2010). A three-step synthetic approach to asymmetrically functionalized 4H-cyclopenta[2,1-b3,4-b′]dithiophenes. Journal of Organic Chemistry, 75(21), 7202-7209. https://doi.org/10.1021/jo101405j
Van Mierloo, Sarah ; Adriaensens, Peter J. ; Maes, Wouter ; Lutsen, Laurence ; Cleij, Thomas J. ; Botek, Edith ; Champagne, Benoît ; Vanderzande, Dirk J. / A three-step synthetic approach to asymmetrically functionalized 4H-cyclopenta[2,1-b3,4-b′]dithiophenes. In: Journal of Organic Chemistry. 2010 ; Vol. 75, No. 21. pp. 7202-7209.
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A three-step synthetic approach to asymmetrically functionalized 4H-cyclopenta[2,1-b3,4-b′]dithiophenes. / Van Mierloo, Sarah; Adriaensens, Peter J.; Maes, Wouter; Lutsen, Laurence; Cleij, Thomas J.; Botek, Edith; Champagne, Benoît; Vanderzande, Dirk J.

In: Journal of Organic Chemistry, Vol. 75, No. 21, 05.11.2010, p. 7202-7209.

Research output: Contribution to journalArticle

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