Chemistry of Four-Membered Ring Compounds Containing a Hypervalent Sulfur Atom and a Heteroatom at the Neighbor Positions
Chemistry of Four-Membered Ring Compounds Containing a Hypervalent Sulfur Atom and a Heteroatom at the Neighbor Positions
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DOI：
10.1080/10426507.2010.508293
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发表时间：
2011-05
期刊：
影响因子：
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通讯作者：
T. Kawashima
中科院分区：
文献类型：
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作者：
T. Kawashima
摘要含四配位和五配位硫与氧、氮或硫的标题化合物已成功合成为稳定化合物。它们含有马丁配体，众所周知，马丁配体能够稳定这种高度配位的主基化合物。x射线晶体学分析显示它们具有扭曲的三角双锥体（TBP）或伪TBP结构。13-15族元素类似物在加热时产生相应的烯烃，与之形成鲜明对比的是，含氧或氮原子的化合物的热分解产生相应的氧烷或叠氮，这表明这些化合物可能是硫酰与羰基化合物或亚胺的Corey-Chaykovsky反应的中间产物。1λ4,2-二硫烷的热裂解也得到相应的硫烷。还描述了这些三元环化合物形成的立体化学（构型保留）。
Abstract Title compounds containing tetracoordinated and pentacoordinated sulfur together with oxygen, nitrogen, or sulfur were successfully synthesized as stable compounds. They contain the Martin ligand, which is well known to be able to stabilize such highly coordinated main group compounds. X-ray crystallographic analyses revealed that they have distorted trigonal bipyramidal (TBP) or pseudo-TBP structures. In marked contrast to group 13–15 element analogues, which afford the corresponding alkenes upon heating, thermolyses of compounds bearing an oxygen or nitrogen atom gave the corresponding oxiranes or aziridine, suggesting the possibility that these compounds are intermediates of the Corey-Chaykovsky reaction of sulfur ylides with carbonyl compounds or imines. Thermolysis of 1λ4,2-dithietanes also gave the corresponding thiiranes. The stereochemistry (retention of configuration) of formation of these three-membered ring compounds is also described.