Study On The Processes Of Synthesis Of Alkenyl Sulfides And Their Reaction With Diarylphosphine Oxides

Alkenyl sulfides are not only an important compound widely existing in biological active molecules and natural products,but also a class of common intermediates in organic synthesis.Therefore,it is of great significance to development a new synthesis method of alkenyl sulfide and its application in organic synthesis chemistry.On the other hand,organic phosphoric compounds are widely used as drugs,agricultural chemicals and chiral ligands.Therefore,it also has important research value.In this paper,a green synthetic method of alkenyl sulfides from alkynes with thiophenols and thiols was developed.Then,the reductive cross coupling reaction between alkenyl sulfides and diarylphosphine oxides was studied.The detailed results are outlined as follows:1.Synthesis of alkenyl sulfides from alkynes with thiophenols and thiolsThe synthesis of alkenyl sulfides from thiophenols,thiols and alkynes was established.The results showed that the reaction could be completed in a short time at room temperature without solvent,catalyst.The alkenyl sulfides was synthesized with the yield up to 98%.The reaction showed good tolerance toward various thiophenols,thiols and alkynes.In addition,this process has some good merits,such as simple operation,environment friendly process and high atom economy.2.Reductive cross coupling reaction of alkenyl sulfides and diarylphosphine oxidesThe reductive cross coupling reaction between alkenyl sulfides and diaryl phosphines was developed,utilizing toluene as solvent and potassium tert-butoxide as base,the target product can be obtained after 24 h reaction at 120℃.The reactions of various alkenyl thioethers with organic phosphine oxides were examined.And it was found that most alkenyl thioethers could react with diaryl phosphine oxides with the yield of 51-89%.This new reaction can break the C-S bond and construct the C-P bond without transition metal catalyst,and futher reduce the C-C double bond.The reaction products were strictly characterized with ¹H NMR,¹³C NMR and HRMS.