碘催化下磺酰肼对氧化吲哚的高区域选择性硫醚化反应  

Iodine-catalyzed Highly Regioselective Sulfenylation of Oxindoles with Sulfonyl Hydrazides

作　　者：王福祥 陈蔚林[1] 申雁 曹泳 WANG Fu-xiang;CHEN Wei-lin;SHEN Yan;CAO Yong(Anhui Research Institute of Chemical Industry,Hefei 230041,China)

机构地区：[1]安徽省化工研究院

出　　处：《安徽化工》2019年第4期41-44,共4页Anhui Chemical Industry

摘　　要：相较于传统硫醚化试剂,磺酰肼价廉易得,通常以固体的形式存在,无恶臭气味,对空气和水稳定,易于实验操作。由于肼基的存在,磺酰肼中硫原子价态的降低并不需要外加的还原剂。首次报道了磺酰肼与氧化吲哚的硫醚化反应。在30 mol%碘的存在下,N,3,3-三取代氧化吲哚可以与芳基磺酰肼发生硫醚化反应,区域选择性极高。此外,该硫醚化反应条件成功地拓展到二氢喹啉酮,但不适于非环状N-酰基苯胺。拓展了磺酰肼硫醚化反应的应用范围,为氧化吲哚的选择性结构修饰提供了新方法。When compared to traditional sulfenylating agents,sulfonyl hydrazides are much more amenable to handling because,in general,they are readily accessible solids,free of unpleasant odor,and compatible with air and water. Owing to the presence of the hydrazinyl group,the decreased valence of the sulfur atom does not require an external reductant. Here we report an unprecedented sulfenylation reaction of oxindoles with sulfonyl hydrazides. In the presence of 30 mol% iodine,a range of N,3,3- trisubstituted oxindoles underwent sulfenylation with arylsulfonyl hydrazides with very high regioselectivity. The sulfenylation reaction conditions were successfully extended to dihydroquinolinones,but not to acyclic N- acylanilines. This study not only extends the scope for the application of sulfonyl hydrazides as sulfenylating agents,but also provides a new method for selective structural modification of oxindoles.

关 键 词：氧化吲哚 磺酰肼 硫醚化反应 区域选择性 

分 类 号：TQ252[化学工程—有机化工]