| Heterocyclic compounds are important skeletons of many organic compounds,which are widely used in the fields of organics,medicine and materials.There have already existed many researches on the synthesis of nitrogen,oxygen,and sulfur heterocycles,while the studies on phosphorus heterocycles were less.In this dissertation,a palladium catalyzed synthesis of aryl-phosphorus bromides and iodo aromatics was described.A series of six-membered and seven-membered phosphorus heterocyclic compounds were obtained by this reaction.1.With bromomethyl diphenylphosphonium oxide and polysubstituted aryl iodide as substrates,palladium acetate as catalyst,tris(3,5-xylyl)phosphine as ligand,cesium carbonate as base,norbornene and trimethylacetic acid as additives,a series of six-membered phosphorus heterocyclic compounds were synthesized.After a norbornene-assisted ortho-C-H activation and a C(sp2)-H direct activation,the cyclic compound was synthesized in the from of intermolecular cross-coupling.This reaction adopted a one-pot method,proceded with good functional group compatibility and the reactants can be easily obtained.2.With(2-bromophenyl)diphenyl phosphine oxide and polysubstituted aryl iodide as the substrate,palladium acetate as catalyst,triphenyl phosphine as ligand,cesium carbonate as base,norbornene and trimethylacetic acid as additives,a series of seven-membered phosphorus heterocyclic compounds were synthesized.This reaction provides a new approach to synthesize seven-membered phosphorous heterocycles2.With(2-bromophenyl)diphenyl phosphine oxide and polysubstituted aryl iodide as the substrate,palladium acetate as catalyst,chiral monophosphine compound of the MOP skeleton as ligand,asymmetric seven-membered phosphorus heterocyclic compounds can be synthesized.This method can be used to synthesize phosphorus-chiral seven-membered heterocyclic compounds. |
