Study On Synthesis Of Sulfonyl(Arylthio)Compounds From The Radical Reaction Of Oxygen-Containing Enynes

Chemists pay much attention to sulfones for their broad applications in organic synthesis.Enyne is one of the important reagents to synthesizing cyclic compounds.Various heterocyclic compounds can be obtainded by radical tandem cyclization.Compared to monofunctional reaction of alkene,doublefunctional reaction can obtain more complicated compounds and have many unique and natural advantages.The main work of this thesis is divided into three parts,in which the radical reactions of oxygen-containing enynes with three different radical reagents to achieve sufonyl and arylthio derivatives are well reported.In the section one,a series of 1-(((E)-2,3-diiodoallyl)oxy)-2-((E)-3-(phenylsulfonyl)allyl)benzene derivatives were provided in acetonitrile by the radical reaction of oxygen-containing 1,8-enynes with sodium sulfinates and iodine.Tert-butyl hydrogen peroxide plays the role of oxidant in the reaction.In addition,vinyl sulfone derivatives can be atom-enconomically synthesized by one-pot reaction under metal-free condition.Sequently,a novel strategy for synthesis of chromene dervatives via metal-free radical annulation reaction of oxygen-containing 1,7-enynes with thiosulfonates has been developed in the section two.The reaction shows broad substrate scope,wide functional group tolerance,and moderate to excellent yields.Moreover,thiosulfonates were well driven to achieve the bifunctionalization reaction of oxo-1,7-enynes which derived from aliphatic alkynes.In addition,the(E)-configuration of the products was highly controlled by the stucture of 1,7-enyne.In the last section,a series of thioether derivatives containing hydroxyl groups was synthesized from the reaction of oxygen-containing 1,7-enyne with disulfide in tetrahydrofuran.Iodine plays the role of oxidant in this efficient bifunctional reaction of double bond.This strategy has the characteristics of mild condition and broad substrate scope.Moreover,all the compounds were characterized by nuclear magnetic resonance,and high resolution mass spectrometry.Some compounds were further confirmed by single-crystal X-ray diffraction,and the corresponding mechanism was proposed for each reaction process.