Discovery Of Several New Reactions Involving Activated Sulfoxide And Nitrosobenzene

Activated sulfoxide is a class of reagents with ultra-high electrophilicity;Nitrosobenzene is a class of reagents that can form C-N bonds or C-O bonds under different conditions.Focuseed research on the new possibility of directly converting C-H bonds into C-C bonds and C-X(X= N,O)bonds.We designed the reactions between activated sulfoxide and olefins under basic conditions to generated sulfur ylides in situ,followed by react with methylenemalonitriles or nitrosobenzenes.We also explored the reaction between nitrosobenzenes and enol salts of lactones in view of the new possibility of molecular editing of carbon-reducing.Firstly,this study proposes the allylic C-H bonds cyclopropaneation and alkylation involving activated sulfoxide,and a new method for the synthesis of vinyl cyclopropanes without transition metal catalysis was developed.The reaction design involves the reaction of olefins and activation of diphenylsulfoxide by triflic anhydride,which subsequently converted to sulfur ylides under basic conditions,and then reacted with arylmethylenemalonitriles to obtain vinyl cyclopropanes.The reaction was carried out in one pot,and the C-H bonds of the allyl position were converted into C-C bonds in the cyclopropanes,with a wide range of substrates,good yield,and good stereoselectivity.When the aryl methylenemalononitriles were replaced with alkyl methylenemalononitriles,the alkylation of allylic C-H bonds can be realized by activated sulfoxide.When the electrophilic substrate was replaced with nitrosobenzene and its derivatives,the vinylogous formamides products were accidentally obtained,which equivalents to constructing new C=O bonds and C-N bonds in a one pot reaction starting from the C-H bonds of olefins via sulfur ylide intermediates.The yield of this reaction needs further optimized.We also studied the reactions between a series of enol salts of lactones and nitrosobenzenes in order to achieve a new molecular editing reaction of carbon reduction,but this part of work has not yet made breakthroughs progress.