Pimkov Igor V, Nigam Archana, Venna Kiran, Fleming Fraser F, Solntsev Pavlo V, Nemykin Victor N, Basu Partha
Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, PA 15282.
Department of Chemistry, The University of Minnesota-Duluth, Duluth, MN 55812.
J Heterocycl Chem. 2013 Jul;50(4):879-886. doi: 10.1002/jhet.1715.
The bicyclic pyran thiolone tetrahydro-3αH-[1,3]dithiolo[4,5-β]pyran-2-thione () engages in a highly unusual fragmentation in the presence of DDQ. The pyran thiolone, , was synthesized by chlorination of 3,4-dihydro-2H-pyran (), followed by condensing with CS and NaSH. Reaction of with DDQ generates the isomerized pyran thiolone tetrahydro-3αH-[1,3]dithiolo[4,5-β]pyran-2-thione () and 4-benzyl-5-(3-hydroxypropyl)-1,3-dithiole-2-thione () via a deep-seated rearrangement. The identity of was confirmed by single crystal X-ray analysis: P2/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 . Collectively, these results establish fundamental reactivity patterns for further research in this area.
双环吡喃硫酮四氢-3αH-[1,3]二硫杂环戊烯并[4,5-β]吡喃-2-硫酮（）在DDQ存在下会发生一种非常不寻常的裂解反应。吡喃硫酮，，是通过对3,4-二氢-2H-吡喃（）进行氯化，然后与CS和NaSH缩合而合成的。与DDQ反应通过深度重排生成异构化的吡喃硫酮四氢-3αH-[1,3]二硫杂环戊烯并[4,5-β]吡喃-2-硫酮（）和4-苄基-5-(3-羟丙基)-1,3-二硫杂环戊烯-2-硫酮（）。通过单晶X射线分析确定了的结构：P2/c，a = 5.807(9) Å，b = 12.99(2) Å，c = 11.445(15)，β = 113.23(6)°。利用机理实验和计算分析来解释在非常不寻常的的形成过程中可能发生的一系列事件。总的来说，这些结果为该领域的进一步研究建立了基本的反应模式。
