Dithiolopyranthione synthesis, spectroscopy, and an unusual reactivity with DDQ

Igor V. Pimkov, Archana Nigam, Kiran Venna, Fraser F. Fleming, Pavlo Solntsev, Victor N. Nemykin, Partha Basu

Research output: Contribution to journalArticlepeer-review

6 Scopus citations

Abstract

The pyranodithiolone rearranges to a more stable isomer and the pyran ring opens up in the presence of DDQ. The bicyclic pyran thiolone tetrahydro-3αH-[1,3]dithiolo[4,5-β]pyran-2-thione (3a) engages in a highly unusual fragmentation in the presence of DDQ. The pyran thiolone, 3a, was synthesized by chlorination of 3,4-dihydro-2H-pyran (1) followed by condensing with CS2 and NaSH. Reaction of 3a with DDQ generates the isomerized pyran thiolone tetrahydro-3αH-[1,3]dithiolo[4,5-β]pyran-2-thione (3b) and 4-benzyl-5-(3-hydroxypropyl)-1,3-dithiole-2-thione (4) via a deep-seated rearrangement. The identity of 3b was confirmed by single crystal X-ray analysis: P21/c, a = 5.807(9) Å, b = 12.99(2) Å, c = 11.445(15), β = 113.23(6)°. Mechanistic experiments and computational insight is used to explain the likely sequence of events in the highly unusual formation of 4. Collectively, these results establish fundamental reactivity patterns for further research in this area.

Original languageEnglish (US)
Pages (from-to)879-886
Number of pages8
JournalJournal of Heterocyclic Chemistry
Volume50
Issue number4
DOIs
StatePublished - Jul 1 2013

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