Electrocatalytic 1,2-Diamination And Oxidative Amination Of Alkenes

Nitrogen-containing compounds,which are widely existed in natural products,have held the balance in pharmaceutical chemistry,in which they often displayed excellent physiological activity.Besides,owing to their strong coordination ability,they are widely employed as ligands in catalytic reactions as well.In virtue of the importance of nitrogen-containing compounds,it is of practical significance to develop atom economic and efficient strategies to construct novel and complex structures more expeditiously.Organic electrochemistry as one of the most important part of modern organic synthesis,which can effectively produce radicals and radical ions as versatile synthetic intermediates.Moreover,indirect electrolysis combines the features of electrocatalysis with organocatalysis,metal catalysis and other strategies,which also has excellent practical prospects in the synthesis of nitrogen-containing compounds.In this thesis,the 1,2-diamination of alkenes and oxidative amination of alkenes were realized by indirect electrolysis.In the first part,we have used triarylamines as organic redox catalysts to convert stable,easily available aryl alkenes with sulfamides to 1,2-diamines,the reaction possesses excellent diastereoselectivity.Monosubstituted sulfamides react in a regioselective manner to afford 1,2-diamines bearing different substituents on the two amino groups.The 1,2-diamination not only obviates the use of any transition metal catalyst and oxidizing reagent,but also ensures broad reaction compatibility with a variety of electronically and sterically diverse substrates.After deprotection of theses cyclic sulfamides furnished diamines which are particularly valued in synthetic chemistry.In the second part,we have employed tailored cobalt-salen complexes as catalysts,which oxidize the substrate to the corresponding nitrogen radical,and initiate radical cyclization and convert the cyclized alkyl radical to the alkene product.The reactions have broad compatibility with a diverse range of functional groups and alkene substitution patterns,and also enabled the efficient synthesis of various high-value alkene-bearing cyclic structures.