State Key Laboratory of Chemical Resource Engineering, Department of Organic Chemistry, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China.
Molecules. 2019 Jul 19;24(14):2628. doi: 10.3390/molecules24142628.
The intramolecular C-H insertions of carbenes derived from 2-diazo-2-sulfamoylacetamides were studied. 2-Diazo-2-sulfamoylacetamides were first prepared from chloroacetyl chloride and secondary amines through acylation followed by sequential treatments with sodium sulfite, phosphorus oxychloride, secondary amines, and 4-nitrobenzenesulfonyl azide. The results indicate that: (1) 2-diazo--dimethyl-2-(-diphenylsulfamoyl)acetamide can take the formal aromatic 1,5-C-H insertion in its -phenylsulfonamide moiety to afford the corresponding 1,3-dihydrobenzo[]isothiazole-3-carboxamide 2,2-dioxide derivative; (2) no aliphatic C-H insertions occur for 2-diazo-2-(-dialkylsulfamoyl)acetamides; and (3) for 2-diazo--phenyl-2-(-phenylsulfamoyl)acetamides, the formal aromatic 1,5-C-H insertion in the -phenylacetamide moiety is favorable to afford the corresponding 3-sulfamoylindolin-2-one derivatives as sole or major products. The intramolecular competitive aromatic 1,5-C-H insertion reactions of 2-diazo-2-sulfamoylacetamides with aryl groups on both amide and sulfonamide groups reveal that the -aryl substituents on acetamide are more active than those on sulfonamide. The chemoselectivity is controlled by electronic effect of the aryl group.
研究了源自 2-重氮-2-磺酰胺基乙酰胺的卡宾的分子内 C-H 插入反应。首先通过酰化将氯乙酰氯与仲胺反应，然后用亚硫酸钠、氧氯化磷、仲胺和 4-硝基苯磺酰叠氮连续处理，制备 2-重氮-2-磺酰胺基乙酰胺。结果表明：（1）2-重氮--二甲基-2-（-二苯磺酰胺基）乙酰胺可以在其-苯磺酰胺部分进行形式的芳基 1,5-C-H 插入，得到相应的 1,3-二氢苯并[]异噻唑-3-甲酰胺 2,2-二氧化物衍生物；（2）2-重氮-2-（-二烷基磺酰胺基）乙酰胺没有发生脂肪族 C-H 插入；（3）对于 2-重氮--苯基-2-（-苯磺酰胺基）乙酰胺，-苯乙酰胺部分的形式芳基 1,5-C-H 插入有利于得到相应的 3-磺酰胺基吲哚啉-2-酮衍生物作为唯一或主要产物。2-重氮-2-磺酰胺基乙酰胺与酰胺和磺酰胺基团上的芳基的分子内竞争性芳基 1,5-C-H 插入反应表明，乙酰胺上的-芳基取代基比磺酰胺上的更活跃。化学选择性受芳基的电子效应控制。
