Synthesis Of Aryl Sulfides From Thiophenol Response Research

Thioethers are an important class of sulfur-containing compounds,which play a huge role in natural products,functional materials and medicines,and can also be used as intermediates for the synthesis of other important biologically active organic sulfones or sulfoxides.Therefore,the construction of C-S bonds has always been the focus and hotspot of organic synthetic chemistry research.On the other hand,cyclohexanone is a class of chemically stable and bulky chemical raw materials,and the use of non-aromatic cyclohexanone compounds as an aryl source has attracted extensive attention of organic synthesis workers.In recent years,our research group has developed a variety of metal-free reactions for the dehydroaromatization of cyclohexanone to construct C-C bonds,C-N bonds and C-S bonds.Based on the previous research,this paper uses cyclohexanone and thiophenol,as raw materials to synthesize aryl sulfide compounds.The research content mainly includes the following two parts:1.A class of reactions for the synthesis of diaryl sulfides using cyclohexanone and thiophenol as raw materials has been developed.This reaction provides an aryl source through the oxidative dehydrogenation of non-aromatic cyclohexanone under the condition of green oxidant oxygen.When cyclohexanone was used as the starting material,the C-S bond was constructed by in-situ deoxygenation of carbonyl group and α-thiolation;when 1,4-cyclohexanedione was used as the substrate,4-hydroxyphenyl sulfide compounds were synthesized by in-situ deoxygenation of carbonyl group and in-situ thiolation.The reaction substrate has a wide adaptability and provides a new synthetic route for the synthesis of aryl sulfide compounds.2.A three-component synthesis reaction of cyclohexanone,amine and thiophenol promoted by iodosuccinimide(NIS)for the synthesis of o-aminothioethers was developed.The reaction achieves the bifunctionalization of the cyclohexanone carbonyl group and the α-position with good chemical and regioselectivity.The method has mild conditions,simple operation and good functional group tolerance.At the same time,the corresponding products can be further transformed into phenothiazine compounds.