The Study Of Coordination Characteristics And Application Of Metal Amidophosphanes Complexes

In this thesis,we will design and synthesize a series of amino acidsand 1,2-cyclohexanediamine-derived aminophosphane ligands,which coordinate with the transition metal to form a new catalytic systems.The catalytic system was applied in the asymmetric [3+2] cycloaddition reaction.?1?As the starting materials of the amino acids and cyclohexanediamine,we have designed and synthesized ten mono-amino acids-derived aminophosphanes,six double-aminoacids-derived aminophosphanes,and four cyclohexanediamine-amino acids-derived aminophosphane ligands.?2?The different skeleton aminophosphane ligands were applied in asymmetric [3+2] cycloaddition reaction of azomethine ylides with electron-deficient alkene.The effects of ligands,metals,solvents and additives on the catalytic performance of the catalysts were studied.The ligands 1g,1p and 1t were respectively identified as the optimal ligand,Ag₂CO₃ as most suitable metal,and toluene and Et3 N as the best solvents and additives.Under the optimal conditions,the substrate adaptation of the [3+2] cycloaddition reaction was studied.The results showed that the reaction had a very good substrate adaptability,and thirty-three highly substituted pyrrolidine derivatives were synthesized withonly endo-diastereoselectivities and up to 98% enantioselectivities.?3?A series of mono-amino acid-derived aminophosphane ligands were also applied in the aldol reaction of the isocyanoacetates with different series of aldehydes.The optimum reaction conditions were found by optimizing the reaction conditions of metal and solvent.The most suitable conditions were Ag2 O and ethyl acetate,respectively.Under the optimal conditions,the substrate adaptability was extended,and twelve highly substituted aldol products were synthesized.The catalytic system was applied in the synthesis of 2-amino-2-deoxy-D-arabinose and 2-deoxy-D-ribose with up to 93:7 enantioselectivity.In addition,a piperidinium acetate-catalyzed method was developed for the Knoevenagel and O-Micheal cascade reaction ofo-hydroxyphenyl-?-diketoes with different series of aldehydes.Inthe presence of piperidinium acetate,sixteen 2,3-disubstitutedchroman-4-ones and nine 2,2-disubstituted benzofuran-3-ones were obtained in moderate to good yields,and the cascadereaction displayed better substrate adaptability.Then,the fluorescence properties of 2,3-Disubstituted Chroman-4-onein combination with metal Eu were studied.Furthermore,anovel type of red fluorescent material was synthesized with potential application.