Moody Christopher J, Slawin Alexandra M Z, Willows David
School of Chemistry, University of Exeter, Stocker Road, Exeter, UK EX4 4QD.
Org Biomol Chem. 2003 Aug 7;1(15):2716-22. doi: 10.1039/b305698h.
Dirhodium(II) tetraacetate catalysed reaction of the indoline diazo thioamide 8 gives the thioisomünchnone 9, a stable characterisable solid. This masked thiocarbonyl ylide undergoes 1,3-dipolar cycloaddition with N-methylmaleimide and maleic anhydride to give the exo-cycloadducts 10 and 11, characterised by X-ray crystallography. The thioisomünchnone 18, derived from diazo thioamide 17, is an extremely stable crystalline mesoionic system which can be characterised by X-ray crystallography but fails to undergo intramolecular cycloaddition. The related thioisomünchnone 19 can be generated by reaction of indoline-2-thione 7 with bromoacetyl chloride in the presence of triethylamine, and undergoes cycloaddition to give adducts 20 and 21.
二醋酸二铑（II）催化吲哚啉重氮硫代酰胺8的反应生成硫代异缪烯酮9，一种稳定的可表征固体。这种掩蔽的硫羰基叶立德与N - 甲基马来酰亚胺和顺丁烯二酸酐发生1,3 - 偶极环加成反应，生成外式环加成产物10和11，通过X射线晶体学进行表征。由重氮硫代酰胺17衍生的硫代异缪烯酮18是一种极其稳定的结晶介离子体系，可通过X射线晶体学进行表征，但不能发生分子内环加成反应。相关的硫代异缪烯酮19可通过吲哚啉 - 2 - 硫酮7与溴乙酰氯在三乙胺存在下反应生成，并发生环加成反应生成加合物20和21。
