A new method for the preparation of 2-thio substituted furans by methylsulfanylation of γ-dithiane carbonyl compounds

Albert Padwa, Cheryl K. Eidell, John D. Ginn, Michael S. McClure

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19 Citations (Scopus)

Abstract

Several related methods for the preparation of differentially substituted 2-thiofurans are described. The general procedure involves the formation of a thionium ion from a γ-dithianyl substituted carbonyl compound followed by cyclization of this reactive intermediate onto the tethered carbonyl group. Two methods for thionium ion generation were explored. One of these involved an acid-catalyzed reaction of β-ketenedithioacetals, prepared from the condensation of 2,2-bis(methylsulfanyl)acetaldehyde with a variety of ketones. Cyclization followed by loss of methane thiol gave 2-thiofurans 17, 18 and 23, 24 in 70-90% yield. Attempts to prepare 5-heteroatom substituted 2-thiofurans from the corresponding β-ketenedithioacetal amides or esters were unsuccessful, leading to 1,2-thio rearranged products. A more successful route involved the reaction of β-acetoxy-γ-thianyl carbonyl compounds with dimethyl(methylthio)sulfonium tetrafluoroborate (DMTSF). Treatment of the dithiane with this reagent resulted in the smooth generation of a thionium ion. Cyclization followed by loss of acetic acid afforded thiofurans 17, 18, 23, 47-49, 51, and 61-64 in 40-100% yield. The N-butenyl substituted thioamido furan furnished a rearranged hexahydropyrroloquinolin-2-one in high yield when heated at 110 °C.

Original languageEnglish (US)
Pages (from-to)1595-1606
Number of pages12
JournalJournal of Organic Chemistry
Volume67
Issue number5
DOIs
StatePublished - Mar 8 2002

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Furans
Carbonyl compounds
Cyclization
Ions
Acetaldehyde
Methane
Ketones
Sulfhydryl Compounds
Amides
Acetic Acid
Condensation
Esters
Acids
thionium
dithiane

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

A new method for the preparation of 2-thio substituted furans by methylsulfanylation of γ-dithiane carbonyl compounds. / Padwa, Albert; Eidell, Cheryl K.; Ginn, John D.; McClure, Michael S.

In: Journal of Organic Chemistry, Vol. 67, No. 5, 08.03.2002, p. 1595-1606.

Research output: Contribution to journalArticle

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