Difluoroalkylation And Alkenylation Of Aryl Sulfoxides Through [3,3]-Rearrangement

[3,3]-Sigmatropic rearrangement is a powerful process in organic synthesis.In the past few years,the [3,3]-rearrangement of aryl sulfoxides with certain nucleophiles via the construction of unstable rearrangement precursors has been greatly advanced.This type of reactions proceeds under catalyst-and metal-free conditions and has become a powerful synthetic tool.Difluoroalkyl group is widely used in the structure modification of bioactive compounds and drugs,because this group can act as a more lipophilic isostere of the carbinol,thiol,hydroxamic acid or amide groups.Difluoroalkylation and alkenylation of aryl sulfoxides through [3,3]-rearrangement are described in the thesis.1.Rencently,our group developed the [3,3]-rearrangement of aryl iodanes with difluoroenol silicone ether,and found that difluoroenol silyl ether showed unique fluorine effect in the rearrangement reactions.Inspired by this,this chapter describes the [3,3]-σ rearrangement reaction of aryl sulfoxide with difluoroenol silyl.It is worthy to notethat the reaction not only shows good functional group compatibility,but also hasexcellent region-and stereoselective and be competenet to elaborate complex molecules in late stage.2.A novel arylation of α,β-unsaturated nitriles with aryl sulfoxides via [3,3]-rearrangement involving an Morita-Baylis-Hillman(MBH)process was disclosed recently by our group.Based on this strategy,the MBH rearrangement reaction of aryl fluoroalkyl sulfoxides with α,β-unsaturated nitriles was developed.The reaction allows the incorporation of both an alkene group and a generally bioactive fluoroalkyl sulfur group into arenes.Furthermore,the reaction features mild conditions and excellent functional group compatibility which highlights the practicality of the method.