Synthesis Of Planar Chiral (4, 12)-Imino[2.2] Paracyclophanyl Dihydroimidazoliums

A remarkable characteristic of paracyclophane is of planar chirality.Being of chiral source,it has attracted great research interests to chemists.By introducing the heteroatoms,such as phosphor,nitrogen,oxygen,and sulphur into paracyclophane, the chiral paracyclophane-based complexes formed with transition metals,already displayed good catalytic effect in asymmetry synthesis and reaction.Imidazoliums and imidazoliniums,the precursors of N-heterocyclic carbenes,combined with transition metals have been used to catalyze the reaction of forming C-C,C-H,C-O, C-N,and olefin metathesis.As the special properties of paracyclophane-based N-heterocyclic carbenes,the new complexs will offer lots of character which differ from either the paracyclophane or the N-heterocyclic carbenes.Therefore,the research of chiral paracyclophane-based N-heterocyclic carbenes has significant and profound meaning in developing the asymmetric catalyst and the asymmetric catalytic reaction.The primary content of this thesis has nine parts:The first part is preparation of[2.2]paracyclophane.At 80-90℃in DMSO,para-methylbenzyl(N,N,N-trimethyl)ammonium chloride reacted with sodium hydroxide to produce[2.2]paracyclophane.The second part is preparation of 4,16-dibromo[2.2]paracyclophane.4,16-dibromo[2.2]paracyclophane was obtained by brominating of[2.2] paracyclophane using iron as catalyst.The third part is preparation of 4,12-dibromo[2.2]paracyclophane.4,16-dibromo[2.2]paracyclophane in Dodecanese was heated at 230℃to attain 4,12-dibromo-[2.2]paracyclophaneThe fourth part is preparation of 4-Dibenzophenone imino-12-bromo[2.2] paracyclophane.4-Dibenzophenone imino-12-bromo[2.2]paracyclophane was obtained by treatment of 4,12-dibromo[2.2]paracyclophane with benzophenone imine,in the presence of sodium tertbutoxide and Pd-DPPF catalyst. The fifth part is preparation and resolution of 4-amino-12-bromo[2.2]paracyclophane.4-Dibenzophenone imino-12-bromo[2.2]paracyclophane is hydrolyzed by HCI i n THF to give 4-amino-12-bromo[2.2]paracyclophane.The resolution of 4-amino-12-bromo[2.2]paracyclophane was achieved to produce Rp-(-)-4-amino-12-bromo[2.2]paracyclophane.The sixth part is preparation of Rp-(-)-N,N′-bis(4-bromo-12-[2.2]Paracyclophany ethylene-1,2-diamine.4-amino-12-bromo[2.2]paracyclophane reacted with glyoxal to give Rp-(-)-N,N′-bis(4-bromo-12-[2.2]Paracyclophanyl)glyoxal diimine,which is then reduced by sodium borohydride.The seventh part is preparation of Rp-(-)-N,N′-bis(4-dibenzophenone imino-12 -[2.2]paracyclophanyl)ethylene-1,2-diamine and Rp(+)-N-12-bromo-4-[2.2] paracyclophanyl)-N′-(12-dibenzophenone imino-4-[2.2]paracyclophanyl) ethylene-1,2-diamine.Rp-(-)-N,N′-Bis(4-bromo-12-[2.2]Paracyclophanyl)ethylene-1,2-diamine and Rp(+)-N-(12-bromo-4-[2.2]paracyclophanyl)-N′-(12-dibenzophenone imino-4-[2.2]paracyclophanyl)ethylene-1,2-diamine are obtained by treatment of 4,12-dibromo[2.2]paracyclophane with dibenzophenone imine,sodium terthutoxide and Pd-DPPF catalyst.The eighth part is preparation of Rp(+)-N-(12-R-4-[2.2]paracyclophanyl)-N′-(12-dibenzophenone imino-4-[2.2]paracyclophanyl)ethylene-1,2-diamine.Under Pd-DPPF catalysis in dioxane,Rp(+)-N-(12-bromo-4-[2.2]paracyclophanyl) -N′-(12-dibenzophenone imino-4-[2.2]paracyclophanyl)ethylene-1,2-diamine reacted with 2-methoxyphenyl boronic acid,3-methoxyphenyl boronic acid andα-naphthyl boronic acid,respectively,to gived the desired compounds in good yields.The ninth part is preparation of Rp(-)-N-(12-R-4-[2.2]paracyclophanyl)-N′(12-dibenzophenone imino -4-[2.2]paracyclophanyl)-4,5-dihydroimidazolium tetrafluoroborates. Rp(-)-N-(12-R-4-[2.2]paracyclophanyl)-N′-(12-dibenzophenone imino-4 -[2.2]paracyclophanyl)-4,5-dihydroimidazolium tetrafluorborates were gained from the diamine,triethyl orthoformate and ammoniums tetrafluoroborate.The innovation of this thesis is as follows:1.Rp-(-)-N,N′-Bis(4-bromo-12-[2.2]Paracyclophanyl)ethylene-1,2-diamine was introduced benzophenone imines group.2.Five precursor of N-heterocyclic carbene bearing dibenzophenone imino were synthesized...