Transition Metal Catalyzed The Synthesis Of Chiral Nitrogen Heterocyclic Compounds

There are lots of chiral N-heterocyclic compounds in nature.Chiral N-heterocyclic compounds are widely used in pharmaceuticals and agrochemicals due to its particular biological functions and pharmacological activities.In this dissertation,we mainly focus on synthesizing chiral N-heterocyclic compounds by transition-metal catalyzed asymmetric reactions.The studies are listed as follows:1?With TADDOL-derived phosphoramides as the chiral ligand,a palladium-catalyzed intramolecular arylation of ortho-bromobenzamide ferrocenes has been realized.After further optimization,we finalized the conditions as follows:10 mol%(C3H5)PdCp,20 mol%L12,1.5 eq.K2CO3,1 eq.AdCOOH,with toluene as solvent at 110? for 24 h.At last,we obtained 10 planar chiral N-heterocyclic compounds with high yields(up to 96%yield)and excellent enantioselectivity(up to 94%ee).All products have been characterized by NMR,HRMS and HPLC.The absolute configuration of one product is S,which was assigned by single crystal XRD.2?the intramolecular arylation of(?5-ortho-bromobenzamide-cyclopentadienyl)(?4-tetraphenylcyclobuta-diene)cobalt can be made enantioselective,proceeding with 85%yield and 30%ee.All products were characterized by NMR,HRMS and HPLC.3?5-endo-hydroaminocyclization of ortho-alkynylanilines for the synthesis of C-N axially chiral compound was developed in presence of AuCl and chiral phosphine ligand.This process generated C-N axially chiral products in up to 100%yield and up to 27%ee via the optimization of chiral phosphine ligands and the screening of solvents,temperature and chiral phosphoric acids.