Bi?OTf?₃-catalyzed Synthesis Of ?-carbonyl Thioethers From 3-aryl Propargyl Alcohols

?-carbonyl thioether is an important backbone in organic synthesis.There have been many reports on the preparation of?-carbonyl thioether,in which 1,4-Michael addition is the most commonly used method for constructing?-carbonyl sulfide structures.However,the exploration of new methods for the synthesis of?-carbonyl sulfide structural units remains a very challenging task.In this paper,the tandem reaction of the Meyer-Schuster rearrangement reaction/thia-Michael addition reaction of Bi?OTf?₃ catalyst with 3-arylpropynyl alcohol as substrate was studied.Efficient synthesis of open chain?-carbonyl sulfide compounds.Studies on the range of applications of 3-arylpropynyl alcohols and RSH indicate that the different aromatic rings in the 3-arylpropynyl alcohol and the substituents at the alpha position of the hydroxyl group have an effect on the reaction:at the hydroxyl group a The propynyl alcohol without a large group can be well converted,and the propynyl alcohol and the alkyl propynyl alcohol having a strong electron withdrawing substituent on the aromatic ring cannot be reacted;RSH has a wide application range.When RSH contains a strong electron-withdrawing substituent,the stronger the electron-withdrawing ability of the substituent,the worse the conversion ability of the propynyl alcohol,and the propargyl alcohol can be very good when the substituent is an electron-donating group and an alkyl group.Then,based on the tandem Meyer-Schuster rearrangement/intermolecular Michael addition reaction/intermolecular amine hydrogenation reaction studied by the research group,we tried to replace the nitrogen-containing nucleophile with RSH.The 3-aryl propynyl alcohol,chalcone and RSH three systems are reacted in series.One-pot synthesis of2-??thio?methyl?-1,3,5-triaryl-1,5-dione?-carbonyl sulfide was successfully synthesized using Bi?OTf?₃ as catalyst;When RSH was methoxyanthracene,we successfully isolated the?-carbonyl sulfide.Then,we studied the application range of 3-arylpropynyl alcohol,chalcone,and RSH.The results show that each substrate has a wide range of applications.The above method has the advantages that the raw material propargyl alcohol is easily available,the experimental method and the operation are simple,the by-products are less,the highest yield of the target product is 95%,and the atomic utilization rate can reach 100%.Provides a new synthetic method for the preparation of?-carbonyl sulfide compounds.