Study Of The C-X(C,N) Bond Formation On The Basic Of Acetonitrile Activation

In nature,the compounds bearing C-X(X=C,N,S,etc.)bond widely emerged in drugs,organic materials and natural products.Therefore,it is an important research area to developing simple and effective methods leading to C-X bonds(X=C,N,S and so on)in the synthetic methods and total synthesis of natural products.In this paper,the formations of C-C bond and C-N bond were developed via iodide or oxidant mediated the activation of acetonitrile bearing cyano or methyl.The research contents of this paper include the following two parts:The first part: the electrophilic addition reaction of thiosulfate and olefin involving the participation of acetonitrile bearing cyano via iodide-catalyzed difunctionalization of alkenes to realized the construction of C-C bond and C-N bond with DMSO as oxidant and thiosulfates as thio-reagent leading to ?-acetamido sulfides.The reaction system with these characters of high selectivity,mild reaction conditions and non-metallic catalysis.Besides,the reaction system can also be extended to the synthesis of cyclic ether and lactone by using alcohols,carboxylic acids,and phenol as nucleophlic reagents.The second part: the dehydrogenation coupling reaction of acetonitrile and coumarin.In this part,the synthesis of 3-cyanmethylcoumarins via direct oxidant activation of acetonitrile using TBPB as free-radical initiator with coumarins,especially,we obtained in good yield when the aromatic ring bearing rich-groups(such as methyl,methoxy,N,N-diethyl etc.).At the same time,we synthesized dehydrogenate coupling reaction of acetone and coumarin under similar conditions.In conclusion,the formation of C-X(X=C,N,S and so on)bonds was achieved by activation of acetonitrile bearing cyano and methyl,target product was obtained in good yields.Besides,we have realized the activations of ethanol,acetic acid and acetone under similar conditions.We has been developed simple,effective method for systhesis of corresponding compounds.