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Journal article
Dithiolopyranthione Synthesis, Spectroscopy, and an Unusual Reactivity with DDQ
Journal of heterocyclic chemistry, v 50(4), pp 879-886
01 Jul 2013
PMCID: PMC4200397
PMID: 25328243
Abstract
The bicyclic pyran thiolone tetrahydro-3H-[1,3]dithiolo[4,5-]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-3H-[1,3]dithiolo[4,5-]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)angstrom, b=12.99(2)angstrom, c=11.445(15), =113.23(6)degrees. 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.
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Details
- Title
- Dithiolopyranthione Synthesis, Spectroscopy, and an Unusual Reactivity with DDQ
- Creators
- Igor V. Pimkov - Duquesne UniversityArchana Nigam - Duquesne UniversityKiran Venna - Duquesne UniversityFraser F. Fleming - Duquesne UniversityPavlo V. Solntsev - University of Minnesota, DuluthVictor N. Nemykin - University of Minnesota, DuluthPartha Basu - Duquesne University
- Publication Details
- Journal of heterocyclic chemistry, v 50(4), pp 879-886
- Publisher
- Wiley
- Number of pages
- 8
- Grant note
- 0614785; 0234872 / CHE GM 061555 / National Institutes of Health; United States Department of Health & Human Services; National Institutes of Health (NIH) - USA DBI 0821401 / National Science Foundation; National Science Foundation (NSF) R15GM061555 / NATIONAL INSTITUTE OF GENERAL MEDICAL SCIENCES; United States Department of Health & Human Services; National Institutes of Health (NIH) - USA; NIH National Institute of General Medical Sciences (NIGMS)
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- Chemistry
- Web of Science ID
- WOS:000325924800022
- Scopus ID
- 2-s2.0-84880934785
- Other Identifier
- 991020898394704721
InCites Highlights
Data related to this publication, from InCites Benchmarking & Analytics tool:
- Collaboration types
- Domestic collaboration
- Web of Science research areas
- Chemistry, Organic