Research On The Green Synthesis Method Of Nitrogen And Oxygen Heterocyclic Compounds

Nitrogen-and oxygen-containing heterocycles were widely found in natural products and drug molecule,most of them have good biological activities.Considering its broad application value,constructing heterocyclic compounds skeletons via a green synthesis method is one of the research hotspots in the field of chemistry to study.C-H activation catalyzed by transition metals can efficiently construct various chemical bonds,such as C-C,C-N,C-O,which has been widely used in the synthesis of drugs and other materials.In particular,C-H activation which was assisted by directing group has some obvious advantages of high selectivity,high functional group tolerance and high atom economy,and in line with the concept of green chemistry.This method has attracted wide attention,which is one of the most popular green synthesis methods.Introducing appropriate directing groups,with the catalysis of transition metals,the functionalization of C-H bond of various amine substrates could be realized,providing green synthesis methods of nitrogen-and oxygen-containing heterocycles,this paper is divided into the following three parts:1.The isoindolin-1-ones derivatives were synthesized using trifluoromethanesulfonic amide as a directing group.An efficient synthesis of isoindolin-1-ones derivatives from trifluoromethylsulfonic anhydride-protected benzylamines,with[RuCl₂?p-cymene?₂]₂ as a catalyst by intramolecular C?sp²?-H carbonylation,has been described.Variously substituted benzylamines could be well tolerated in this new protocol,affording the corresponding products in moderate to excellent yields.This method uses commercially available isocyanate instead of traditional CO as a novel carbonyl source to achieve C?sp²?-H carbonylation reaction.2.The isoindolin-1-ones derivatives were synthesized from two different types of carbonyl sources with the assistance of oxalyl amide as a directing group.Part I:The synthesis of isoindolin-1-ones derivatives were synthesized high efficiently via Pd?OAc?₂ catalyzed intramolecular C?sp²?-H carbonylation with oxalyl amide-assisted benzylamines as raw material and ethyl glyoxylate as carbonyl sourc.Part II:Co?OAc?.4H₂O catalyzed C?sp²?-H carbonylation can be realized with oxalyl amide-assisted benzylamines as raw material and diisopropyl azodiformate as carbonyl source,affording the isoindolin-1-ones in moderate yields.3.The Palladium catalyzed intramolecular C-H amination of aryl ethylamine substrates via the assistance of oxalyl amide as a directing group is described,giving a variety of indoline derivatives.A wealth of indoline derivatives could be obtained in good yields using a commercially available oxidant TBPB instead of expensive PhI?OAc?₂.The C-H functionalization of various amine substrates catalyzed by transition metals and assisted by directing groups can construct various heterocyclic compounds skeleton efficiently,and these protocols have the advantages of high chemical selectivity,simple operation,and simple reaction equipment,which are meaningful in green synthesis.