The Synthesis Of Planarchiral Diazaphospholes And The Research Of Azide And Isocyanide Ru~ⅡIntramolecular Addition Reaction

Central chirality, axis chiral and planar chiral catalysis in the field ofasymmetric catalysis have been extensively studied, Planar chiralheterocyclic catalysis is gradually becoming an important element ofthe planar chiral field. Currently heterocyclic part of the planar chiralheterocyclic molecules pyrrole, triazole and pyridine fused ringsystem as the main research. Single heteroatom in the heterocycliclimit the ability of nucleophilic catalysis and coordination mode ofdiversification, reduce the versatility of the catalyst. In this paper, theselected five-membered heterocyclic ring of 1H-3,5-disubstituted-1,2,4-diazaphospholid heterocyclic ligands, planar chiraldiazaphospholid contains both N and P heteroatom, whichcoordination ability and mode are different.This article was also synthesized ligand 1H-3,5-2-isopropyl-1,2,4 -diazophosphine heterocyclic,1H-3,5-diethyl-1,2,4-diazophosphineheterocyclic and 1H-3,5-dimethyl-1,2,4-diazophosphine heterocyclic,and by the sublimation obtained the crystal structure of the 1H-3, 5 -isopropyl-1,2,4-diazophosphine heterocyclic, We also use X-raydiffraction analysis,¹HNMR,¹³CNMR,³¹PNMR to study the structureand composition.Master ligand synthesis method on the basis of the first synthesis of a series of 1H-3,5-disubstituted-1,2,4-diazaphospholid heterocyclicligand and its potassium salt with the Cp^* of Ru（II） synthesized aseries of planar chiral sandwich compounds, one of the complexes[（3-Me-5-tBudp）RuCp^*] has been the single crystal structure usingx-diffraction single-crystal technology to analyze. These planar chiralcomplexes provide an important experimental basis for furtherresearch and application.In addition, complex （RNCN）-ion has a different structure, diversevariety of configurations and metal coordination mode. This articlechose 2,6-dimethyl isocyanide and of Ru （II） to study this series ofreactions , 2,6-dimethyl isocyanide and Cp^*Ru synthetic product withsodium azide substitution reaction Synthesis azido rutheniumcomplexes, azido, and the other isocyanide molecules can be formedtetrazole compounds by 1,3-cycloadditon. Hope that by moving one ofthe isomers, one isomer may migrate through theπbond conversionto the allyl ruthenium intermediate metal atoms from NCN-carbonatoms migrate to the nitrite nitrogen from 1,2-atoms, however, themigration of the 1,2-amino nitrogen atom usually is consideredunlikely because of steric hindrance on the nitrogen atom is too large.This article select the high-temperature conditions to make thismigration smooth the bare RNCN-sandwich compounds of thesandwich compounds [（η5-CpMe₅）Ru（η6-（arene）NCN）], another isomerof tetrazole compounds to remove part of N₂ get a half sandwichcompounds [（η5-CpMe₅）Ru（CNAr）₂（CNCAr）]. Before the two-stepreaction of the two ruthenium complexes, a total of four rutheniumcomplexes, We also use X-ray diffraction analysis,¹HNMR,¹³CNMR to study the structure and composition.