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Unexpected cleavage of thiacalix[4]arene sulfoxides

机译:硫杂杯[4]亚芳基亚砜的意外裂解

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Thiacalix[4]arenes having one bridge oxidized to a sulfoxide moiety can react with organolithium reagents to form cleaved structures which are otherwise difficult to access. Cleavage of the macrocyclic skeleton is independent of the starting conformation as proven by the same product obtained from the corresponding cone, partial cone or 1,3-alternate derivatives. Quenching of the crude reaction mixture with D2O allowed elucidation of the mechanism which is based on the ligand exchange of the sulfoxide functionality. The general applicability of this reaction was demonstrated using the corresponding distal or proximal disulfoxide derivatives, while the quenching of the reaction mixture using various electrophiles allowed the isolation of the corresponding mono- and di-substituted oligomers. The structure of the unexpected product (a tetrameric derivative) was assigned by single crystal X-ray crystallography.
机译:带有一个桥被氧化成亚砜部分的硫杂杯[4]芳烃可以与有机锂试剂反应形成裂解结构,否则很难进入该结构。大环骨架的裂解与起始构象无关,由相应的 cone 部分锥体或1,3- 交替衍生物。用D 2 O淬灭粗反应混合物,可以阐明基于亚砜官能团的配体交换的机理。使用相应的远端或近端二亚砜衍生物证明了该反应的一般适用性,同时使用各种亲电试剂淬灭反应混合物可以分离出相应的单取代和二取代的低聚物。通过单晶X射线晶体学确定了意外产物(四聚体衍生物)的结构。

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