| In organic synthetic reactions,the scope and application of organosulfur chemistry have increased tremendously.?-carbonyl sulfides are an important part of organic sulphides,which plays a key role in organic chemical synthesis.Throughout the existing methods,most of them need to use transition metal catalysis,more demanding reaction conditions,conversion rate is not high and so on.Therefore,the development of new methods to prepare ?-carbonyl sulfides are still the goal pursued by many researchers.In 1997,Montevecchi and his colleagues first studied the reaction of aryl vinyl azides.They found that the reaction of aryl thiols with ?-phenyl vinyl azides almost quantitatively obtained ?-carbonyl sulfides.This is the only report on the reaction of vinyl azide esters with thiol radicals.Therefore,we decided to discuss this reaction again in order to expand the substrate scope and hope to establish a comprehensive and useful method for the preparation of ?-carbonyl sulfide.According to relevant literature,the free radical reaction proposed by Montevecchi and his colleagues is more suitable for the reaction mechanism.On this basis,we first verified the experimental mechanism : we investigated the coupling reaction of phenylallyl azides and p-toluenethiophenol,and whether oxygen was needed.Then the optimal reaction conditions were obtained by condition screening:terminal alkenyl azide and thiol as substrates,tetrahydrofuran as solvent,at 40? air conditions.Then a series of substrate expansions were carried out under the optimal conditions.In the process of substrate expansion,we found that alkyl azides can react with thiols to form ?-carbonyl sulfides.Oligopeptides containing cysteine can also react with azide to form ?-carbonyl sulfide.This method has the advantages of mild reaction conditions,easy operation,simple raw material preparation and wide source,based on vinyl azide can react with cysteine residue,which provides a new method for the modification of cysteine residue. |
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