Synthesis Of Chiral Benzylic Sulfides And N-aroyl Sulfoximines

Thioethers and its derivatives are widely found not only in drug molecules and bioactive molecules,but also in agricultur al chemicalse,dyes and functional polymer materials.Since benzylic thioethers a nd its sulfoximine derivatives are widely used it is of great significance to discover new methods to construct high valued sulfur-containing compounds based on some simple and cheap sulfur-containing compounds.This paper consists of two parts:?1?Synthesis of chiral lbenzylic sulfides with thiophenols and thiols as nucleophiles and chiral benzylic quaternary ammonium salts from in situ reaction of chiral benzylic tertiary amines and methyl triflate;?2?Visible light-promoted oxidative coupling of NH-sulfoximines with aryl aldehydes.The details are described as follows:1.We have developed a method for the synthesis of chiral benzylic sulfides via copper-catalyzed C-S coupling of a series of thiophenols and thiols and chiral benzylic tertiary amines in situ activated by methyl trifluoromethanesulfonate.First,we optimized the reaction conditions to obtain the best reaction conditions.Second,under the optimized reaction conditions,the scope of the reaction was investigated and the enantiomer purity of the products were analyzed by chiral HPLC.Finally,we explored the mechanism-studying experiments and proposed a reasonable mechanism.The synthetic method has the following advantages:no ligand needed,relatively mild reaction conditions,simple operation,a wide scope of substrates,good to excellent yields?75-95%?,and hingly enantiopure products?94-99%ee?.This reaction product maintains excellent ee value even at high reaction temperature.This work provides a efficient methodr for the synthesis of chiral benzylic sulfides.2.We have developed a method for the synthesis of N-aroyl sulfoximines from the thioether-derived NH-sulfoximines and aryl aldehydes.This is a visible light-promoted free radical reaction at room temperature.It does not need metal catalyst or base,and has the merits of simple operation,a broad scope of substrates,good to excellent yield,complete retention of chirality of the sulfoximines in the products,and small environmental harmgreen synthetic process.Reactive free radical species was captured via experiment,and thus base on it.All products are strictly characterized with ¹H NMR,¹³C NMR,HRMS and so on.