Sulfonylation And Sulfenylation With Sulfonyl Hydrazides

Sulfonyl hydrazides are always used as reductants, which is based on the NHNH2group of sulfonyl hydrazides, but the other parts are rarely studied. In this article, the applications of sulfonyl hydrazides are introduced, including recommends of backgrounds of sulfonyl hydrazides as sources of phenyl, sulfonyl and thiol and recommends of their extended applications. We reported a reaction of aerobic oxidative cross-coupling of enantioenriched primary allylic amines with sulfonyl hydrazides leading to optically active allylic sulfones at room temperture, and Cu(Ⅰ) catalyzed C-S coupling of sulfonyl hydrazides with boronic acids to prepare unsymmetrical thioethers which is under studying.This article includes three chapters.Chapter1:Research progress in sulfonyl hydrazides.In this chapter, sulfonyl hydrazides as sources of phenyl, sulfonyl and thiol are introduced from three sections. The previous reports about sulfonyl hydrazides as sources of phenyl mainly focus on reactions of alkenes, electron-rich heterocycles and α,β-unsaturated ketones with sulfonyl hydrazides, to prepare poly substituted alkenes, arylation of heterocycles with ketones. The reports about sulfonyl hydrazides as sources of sulfonyl are reported more than others, principally about the substitution reactions of electron-deficient aromatic compounds with sulfonyl hydrazides, addition reactions of alkenes with sulfonyl hydrazides and rearrangement reactions of tosylhydrazones which are prepared from sulfonyl hydrazides and ketones. There are a few reports about sulfonyl hydrazides as sources of thiol, which are sulfenylation of electron-rich aromatic compounds, alkenes and alkynes.Chapter2:Oxidative cross-coupling of enantioenriched primary allylic amines with sulfonyl hydrazides.The articles on allylation of boronic acids, sulfinate salts and malononitriles with highly enantioenriched allylic amines are reported sequentially, the former two reactions need higher temperature to give products with complete transfer of chirality and complete transformation of chirality separately, while the latter one can react at room temperature. We replace sulfonyl hydrazides of sulfinate salts to react with highly enantioenriched allylic amines, which can also react open to air at room temperature to give allylic sulfones in moderate to excellent yields with excellent retention of ee.Chapter3:Cu(I) catalyzed cross-coupling of sulfonyl hydrazides with boronic acids to prepare thioethersThe articles of preparing unsymmetrical thioethers are widely reported, among these coupling reactions of boronic acids with sulfides are less reported, and cross-coupling reactions of aryl halides with sulfur compounds are reported more, especially the reactions of aryl halides with thiols, which include Pd-catalysis, Cu-catalysis, Fe-catalysis, Ni-catalysis and Rh-catalysis. By using sulfonyl hydrazides instead of thiols, the problem of unpleasant odors was solved easily. We find that sulfonyl hydrazides with boronic acids can prepare unsymmetrical thioethers, which have broad applications in pharmaceutical industry and material science.