Dithiolopyranthione Synthesis, Spectroscopy, and an Unusual Reactivity with DDQ

Dithiolopyranthione Synthesis, Spectroscopy, and an Unusual Reactivity with DDQ

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...

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Veröffentlicht in:Journal of heterocyclic chemistry 2013-07, Vol.50 (4), p.879-886
Hauptverfasser: Pimkov, Igor V., Nigam, Archana, Venna, Kiran, Fleming, Fraser F., Solntsev, Pavlo V., Nemykin, Victor N., Basu, Partha
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container_end_page 886
container_issue 4
container_start_page 879
container_title Journal of heterocyclic chemistry
container_volume 50
creator Pimkov, Igor V.
Nigam, Archana
Venna, Kiran
Fleming, Fraser F.
Solntsev, Pavlo V.
Nemykin, Victor N.
Basu, Partha
description 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.
doi_str_mv 10.1002/jhet.1715
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title Dithiolopyranthione Synthesis, Spectroscopy, and an Unusual Reactivity with DDQ
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