【作者】 邢正伟；

【导师】 马玉道；

【作者基本信息】 山东大学 ， 有机化学， 2008， 硕士

【摘要】 环仿的一个显著特点是具有面不对称性,作为手性源,越来越引起化学家的极大兴趣。在环仿上通过引入磷、氮、氧、硫等杂原子而制得的手性配体,经过与过渡金属形成配合物后,在不对称合成及反应方面都取得了良好的催化效果。氮杂环卡宾前体-咪唑盐和咪唑啉盐,通过与过渡金属形成的金属配合物应用于催化C-C、C-H、C-O和C-N键的形成反应,包括烯烃复分解反应。由于具有环仿的氮杂环卡宾的特殊性,及卡宾上引入基团的性质,使得这种新型配合物表现出许多既不同于环仿又不同于普通氮杂环卡宾的性质。所以,含有手性环仿的氮杂环卡宾配合物的研究对于不对称催化剂和不对称催化反应都有着重大而深远的意义。本论文的主要内容分为九部分,主要内容如下:一.[2.2]对环二甲苯(环仿)的合成在强碱性环境中,对甲基苄基氯化铵中的氯原子被溶液中的羟基所取代,然后在加热条件下,两分子聚合生成[2.2]环仿。二.4,16-二溴[2.2]环仿以溴化铁做催化剂,[2.2]环仿在二氯甲烷和溴素中进行取代反应,得到4,16-二溴[2.2]环仿。三.4,12-二溴[2.2]环仿的合成4,16-二溴[2.2]环仿以正十二烷为溶剂在230℃下转位得到4,12-二溴[2.2]环仿。四.4-溴-12-二苯甲酮亚胺基[2.2]环仿合成由4,12-二溴[2.2]环仿在催化剂Pd-DPPF及强碱叔丁醇钠的作用下,与二苯甲酮亚胺发生偶联反应,制得一取代和二取代的亚胺。五.4-溴-12-氨基[2.2]环仿的合成及拆分4-溴-12-二苯甲酮亚胺基[2.2]环仿在酸性条件下水解为4-溴-12-氨基[2.2]环仿。用左旋樟脑磺酸与水解后的胺成盐进行拆分得到(-)-4-溴-12.氨基[2.2]环仿和(+)-4-溴-12-氨基[2.2]环仿。六.Rp-(-)-N,N′-双(4-溴-12-[2.2]环仿基)乙二醛二亚胺的合成4-溴-12-氨基[2.2]环仿与乙二醛反应可以得到Rp-(-)-N,N′-双(4-溴-12-[2.2]环仿基)乙二醛二亚胺,此二亚胺在硼氢化钠的作用下还原为Rp-(-)-N,N′-双(4-溴-12-[2.2]环仿基)乙二胺。七.Rp(+)-N,N′-双(12-二苯甲酮亚胺基-4-[2.2]环仿基)乙二胺和Rp(+)-N(12-溴4-[2.2]环仿基)-N′-(12-二苯甲酮亚胺基-4-[2.2]环仿基)乙二胺的合成Rp-(-)-N,N′-双(4-溴-12-[2.2]环仿基)乙二胺在催化剂Pd-DPPF及强碱叔丁醇钠的作用下,与二苯甲酮亚胺发生偶联反应,制得一取代和二取代的亚胺。八.Rp(+)-N-(12-R-4-[2.2]环仿基)-N′-(12-二苯甲酮亚胺基-4-[2.2]环仿基)乙二胺Rp(+)-N(12-溴-4-[2.2]环仿基)-N′-(12-二苯甲酮亚胺基-4-[2.2]环仿基)乙二胺在二氧六环和Pd-DPPF的作用下,通过Suzuki反应分别偶联间甲氧基、邻甲氧基和α-萘基。九.Rp-咪唑啉氟硼酸盐的合成Rp(+)-N-(12-R-4-[2.2]环仿基)-N′-(12-二苯甲酮亚胺基-4-[2.2]环仿基)乙二胺用原甲酸三乙酯为关环试剂,与固体氟硼酸胺反应,制备相应的咪唑啉氟硼酸盐。本论文的创新性:一.首次在Rp-(-)-N,N′-双(4-溴-12-[2.2]环仿基)乙二胺分子上引入二苯甲酮亚胺基团。二.合成了五种含有亚胺基的含氮杂环卡宾前体。更多还原

【Abstract】 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更多还原