含亚胺基的（4，12）-位取代环仿基面手性氮杂环卡宾前体的合成研究
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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。
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]paracyclophane
The 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
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。
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]paracyclophane
The 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
引文
1,T.M.Tmka,R.H.Grubbs,The Development of L2X2Ru=CHR Olefin Metathe-sis Catalyst s:An Organometallic Success Story[J],Acc,Chem,Res.,2001,34:18-29.
2,A,J,Arduengo,A stable crystalline carbene[J],J,Am,Chem Soc.,1991,113:361-363.
3,W.A,Herrmann,N-Heterocyclic Carbenes:A New Concept in Organometall-ic Catalysis [J],Angew,Chem,Int,Ed.,2002,41:1290-1309.
4,D,J,Cram,Cyclophane chemistry:bent and battered benzene rings[J].Acc.Chem,Res.,1971,4:204-238.
5,E.L,Popova,V.I,Rozenberg,Z.A,Staikova,H,Hopf,Thermotropic Liquid Crystals from Planar Chiral Compounds:Optically Active Mesogenic[2.2]Par-acyclophan e Derivatives[J],Angew,Chem,Int,Ed.,2002,41:3411-3414.
6,J,Lahann,H,Hocker,R,Langer,Synthesis of Amino[2.2]paracyclophanes-Beneficial Monomers for Bioactive Coating of Medical Implant Materials[J].Angew,Chem,Int,Ed.,2001,40:726-278.
7,S,E,Gibson,J,D,Knight,[2.2]Paracyclophane derivatives in asymmetric catalysis[J],Org,Biomol,Chem.,2003,1:1256-1269.
8,P.J,Dyson,B.F.G,Johnson,C.M,Martin,Ruthenium cluster-[2.2]paracyclophan-e compl exes[J],Coord,Chem,Rev.,1998,175:59-89.
9.A.J.Arduengo,Preparation of 1,3-disubstituted imidazolium salts[P].US,1991,5077414.
10.A.A.Gridnev,I.M.Mihalteseva,Synthesis of l-Alkylimidazoles[J],Syn.Com-mun.,1994,24:1547-1555.
11.A.J.Arduengo,IIIR.Krafczyk,Imidazolylidenes,Imidazolinylidenes and lmid-azo-lidines [J],Tetrahedron,1999,55:14523-14534.
12.F.E.Hahn,L.Wittenbecher,Evidence for an Equilibrium between an N-heter-ocyclic Carb ene and Its Dimer in Solution[J],Angew.Chem.Int.Ed.,2000,39:541-543.
13.D.Enders,K.Breuer,Preparation,Structure,and Reactivity of 1,3,4-Triphenyl-4,5-dihydrolH-1,2,4-triazol-5-ylidene,a New Stable Carbene[J],Angew.Chem.Int.Ed.,1995,34:1021- 1023.
14.D.Ender,K.Breuer,1,3,4-Tdphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene appl-ications of a stable earbene in synthesis and catalysis[J],J,Prakt.Chem.,1997,339:397-399.
15.W.A,Herrmann,N-Heterocyclic Carbenes:A New Concept in Organometalli-c Catalysis [J].Angew.Chem.Int.Ed.,2002,41:1290-1309.
16.W.A.Herrmann,K.Ofele,Oxy Functionalization of Metal-Coordinated Hetero-cyclic Carb enes[J].Organometallics,1995,14:1085-1086.
17.W.A.Herrmann,C.Koeher,N-Heterocyelic Carbene Complexes of Palladium:Well-Defined,Air-Stable,Recyclable Catalysts for the Heck Reaction[J].Chem.Eur.J.,1996,2:772-779.
18.W.Baratta,W.A.Herrmann,Convenient syntheses of novel ruthenium catalysts bearing N-heterocyclic carbenes[J].J.Organomet.Chem.,2000,593:489-493.
19.K.Ofele,W.A.Herrmann,Metal complexes of acyclic diaminocarbenes:links between N-heterocyclic carbene(NHC)and Fischer-carbene complexes[J].J.Organomet.Chem.,2003,684:235-248.
20.I.Huang,S.P.Nolan,Stereoelectronic Effects Characterizing Nucleophilic Carb-ene Ligands Bound to the Cp~*RuCI(Cp~*= 5-C5Me5)Moiety:A Structural And Thermochemical Investigation[J].Organometallics,1999,18:2370-2375.
21.W.A.Herrmann,O.Runte,Synthesis and structure of an ionic beryllium- "car-bene" com plex[J],J.Organomet.Chem.,1995,501:C1-C4.
22.H.Schumann,J.Gottfriedsen,Metallocenes of the alkaline earth metals and t-heir carbene complexes[J],J.Organomet.Chem.,2001,617:588-600.
23.M.H.Voges,C.Romming.Synthesis and Characterization of 14-Electron Cyciop-entadienyi Chromium(Ⅱ)Complexes Containing a Heterocyclic Carbene Liga-nd[J].Organometallics,1999,18:529-533.
24.C.D.Abernathy,A.H.Cowley,Reaction of nickelocene with 1,3-dimesityl imid-azolium chl oride[J],J.Organomet.Chem.,2000,596:3.5.
25.J.C.Garrison,W.J.Youngs,Synthesis and Structural Characterization of an Imi-dazolium-Li nked Cyelophane and the Silver Complex of an N-Heterocyclic Carbene-Linked Cyclophane[J].Organometallics,2001,20:1276-1278.
26.J.Pytkowicz,S.Roland.Synthesis of Chiral silver(I) diaminocarbene complexes from (R,R)-4,5-di-tert-butylimidazoline [J].J.Organomet.Chem.,2001,631:157- 163.
27.R.A.Batey,M.Shen. Carbamoyl-Substituted N-Heterocyclic Carbene Complexes of Palladium(II): Application to Sonogashira Cross-Coupling Reactions [J]. Org. Lett, 2002,4:1411-1414.
28.W.A.Herrmann, M.Elison. Metal Complexes of N-Heterocyclic Carbenes-A New Structural Principle for Catalysts in Homogeneous Catalysis [J]. Angew. Chem. Int.Ed., 1995,34:2371-2374.
29.C.Yang, S.P.Nolan. Highly Efficient Heck Reactions of Aryl Bromides with n-Butyl Ac rylate Mediated by a Palladium/Phosphine-Imidazolium Salt Syste-m[J].Org.Lett.,2001,3:1511-1514.
30.M.B.Andrus,C.Song. Palladium-Imidazolium Carbene Catalyzed Mizoroki-Hec-k Coupling with Aryl Diazonium Ions [J]. Org.Lett.,2002,4:2079-2082.
31 J.A.Loch,R.H.Crabtree,.Palladium Complexes with Tridentate Pincer Bis-Carb-ene Ligands as Efficient Catalysts for C-C Coupling,[J]. Organometallics, 2002,21:700-706.
32.M.B.Andrus,J.Liu. Synthesis of resveratrol using a direct decarbonylative He-ck approac h from resorcylic acid[J].Tetra.Lett.,2003,44:4819-4822.
33.M.Mayr,M.R.Buchmeiser.1,3-Dialkyl- and 1,3-Diaryl-3,4,5,6-tetrahydro pyrimi-in-2-ylidene Rhodium(i) and Palladium(II) Complexes: Synthesis, Structure,and Reactivity [J].Chem.Eur.J.,2004,10:1256-1266.
34.K.Selvakumar, M.Beller.Synthesis of Monocarbenepalladium(0)Complexes and Their Catalytic Behavior in Cross-Coupling Reactions of Aryldiazonium Salts[J]. Chem.Eur.J.,2002,8:3901-3906.
35. C.W.K.Gstottmayr,W.A.Herrmann.A Defined N-Heterocyclic Carbene Compl-ex for the Palladium-Catalyzed Suzuki Cross-Coupling of Aryl Chlorides at Ambient Temperatures[J].Angew.Chem.Int.Ed.,2002,41:1363-1365.
36.G.Altenhoff,F.Glorius, Sterically Demanding. Bioxazoline-Derived N-Heterocy-clic Carbene Ligands with Restricted Flexibility for Catalysis [J]. J.Am.Chem.Soc.,2004,126:15195-1 52001.
37.A.Furstner,A.Leitner.General and User-friendly Method for Suzuki Reactions with Aryl Chlorides[J].Synlett.,2001,2:290-292.
38.O.Navatro,S.P.Nolan,Cross-Coupling and Dehalogenation Reactions Catalyzed By(N-H eterocyclic carbene)Pd(allyl)Cl Complexes[J],J.Org.Chem.,2004,69:3173-3180.
39.O.Navarro,S.P.Nolan,A General Method for the Suzuki-Miyaura Cross-Coup-ling of Ster ically Hindered Aryl Chlorides:Synthesis of Di-and Tri-orthosu-bstituted Biaryls in 2-P ropanol at Room Temperature[J],J.Am.Chem.Soc.,2003,125:16194-16195.
40.M.B.Andrus,C.Song,Palladium-Imidazolium Carbene Catalyzed Aryl,Vinyl,And Alkyl Suzuki-Miyaura Cross Coupling[J],Org.Lett.,2001,3:3761-3764.
41.H.M.Lee,S.P.Nolan.Efficient Cross-Coupling Reactions of Aryl Chlorides and Bromides with Phenyl- or Vinyltrimethoxysilane Mediated by a Palladium/Imidazolium Chloride System[J].Org.Lett.,2000,2:2053-2055.
42.E.Peris,J.A.Loch,Palladium Complexes with Tridentate Pincer bis-Carbene Ligands as Efficient Catalysts for C-C Coupling[J].Chem.Commun.,2001,23:201-204.
43.V.P.W.Bohm,W.A.Herrmann.Nickel-Catalyzed Cross-Coupling of Aryl Chlori-des with Ar yl Grignard Reagents[J].Angew.Chem.Int.Ed.,2000,39:1602-1604.
44.S.Caddick,M.R.V.Williams.An improved synthesis of bis(1,3-di-N-tertbutylimi-dazol-2-ylid ene)palladium(0)and its use in C-C and C-N coupling reactions[J],J.Organomet.Chem.,2001,617:635-639.
45.O.A.Grasa,S.P.Nolan.Palladium/Imidazolium Salt Catalyzed Coupling of Aryl Halides with Hypervalent Organostannates[J],Org.Lett.,2001,3:119-122.
46.A.C.Hillier,S.P.Nolan.Catalytic cross-coupling reactions mediated by palladium/nucleophili c carbene systems[J],J.Organomet.Chem.,2002,653:69-82.
47.P.Espinet,A.M.Echavarren,The Mechanisms of the Stille Reaction[J].Angew.Chem.Int.Ed.,2004,43:4704-4734
48.A.K.Lewis,S.Caddic.Synthetic,Structural,and Mechanistic Studies on the Ox-idative Add ition of Aromatic Chlorides to a Palladium(N-Heterocyclic Carbe-ne)Complex:Relevanc e to Catalytic Amination[J],J.Am.Chem.Soc.,2003,125:10066-10073.
49.J.Huang,S.P.Nolan.General and Efficient Catalytic Amination of Aryl Chlori-des Using a Palladium/Bulky Nucleophilic Carbene System[J],Org.Lett.,1999,1:1307-1309.
50.M.S.Viciu,S.P.Nolan.An Air-Stable Palladium/N-Heterocyclic Carbene Compi-ex and Its Reactivity in Aryl Amination[J].Org.Lett.,2002,4:2229-2231.
51.M.S.Viciu,S.P.Nolan.Synthesis,Characterization,and Catalytic Activity of N-Heterocyclic Carbene(NHC)Palladacycle Complexes[J],Org.Lett.,2003,5:1479-1482.
52.M.S.Viciu,S.P.Nolan.Activation and Reactivity of(NHC)Pd(allyl)Cl(NHC=N-Heterocyclic Carbene)Complexes in Cross-Coupling Reactions[J],Organome-tallics,2002,21:5470-5472.
53.G.A.Grasa,S.P.Nolan.Amination Reactions of Aryl Halides with Nitrogen-Contai-ning Rea gents Mediated by Palladium/Imidazolium Salt Systems[J],J.Org.Chem.,2001,66:7729-7737.
54.S.R.Stauffer,J.F.Hartwig,High Turnover Number and Rapid,Room-Temperat-ure Aminati on of Chloroarenes Using Saturated Carbene Ligands[J].Org.Lett.,2000,2:1423-1426.
55.J.Cheng,M.L.Trudell.Synthesis of N-Heteroaryl-7-azabicyclo[2.2.1]heptane Der-ivatives via Palladium-Bisimidazol-2-ylidene Complex Catalyzed Amination Reactions[J],Org.Lett.,2001,3:1371-1374.
56.B.Gradel,Y.Fort.Nickel-catalysed amination of aryl chlorides using a dihydro-imidazoline carbene ligand[J],Tetra.Lett.,2001,42:5689-5692.
57.C.Desmarets,Y.Fort.Nickel(0)/Dihydroimidazol-2-ylidene Complex Catalyzed Coupling of Aryl Chlorides and Amines[J].J.Org.Chem.,2002,67:3029-3036.
58.a).W.A.Herrmann,J.Schwarz,High-Yield Syntheses of Sterically Demanding Bis-(N-hetero cyclic carbene)Complexes of Palladium[J],Organometallics,1999,18:4082-4089.
b).T.Weskamp,W.A.Herrmann.Combining N-heterocyclic carbenes and phosphines:improve d palladium(Ⅱ)catalysts for aryl coupling reactions[J].J.Organomet.Chem.,1999,585:348-352. c).W.A.Herrmann, J.Schwarz.Homoleptic chelating N-heterocyclic carbine comple-xes of palla dium and nickel [J].J.Organomet.Chem.,1999,575:80-86.
d).V.P.W.Bohm,W.A.Herrmann.N-Heterocyclic carbenes: Part 26. N-Heterocyclic carbene complexes of palladium(0): synthesis and application in the Suzuki cross-coupling reaction [J]. J.Organomet.Chem.,2000,595:186-190.
59.W.A.Herrmann,V.P.W.Bohm.Synthesis, structure and catalytic application of palladium(II) complexes bearing N-heterocyclic carbenes and phosphines [J].J. Organomet. Chem.,2001,617:616-628.
60.T.Weskamp,W.A.Herrmann, A Novel Class of Ruthenium Catalysts for Olef-in Metathes is [J].Angew.Chem.Int.Ed.,1998,37:2490-2493.
61.T.Weskamp,W.A.Herrmann, N-heterocyclic carbenes: novel ruthenium-alkylid-ene complexes,[J]. J.Organomet.Chem.,1999,582,362-365.
62.U.Frenzel,W.A.Herrmann.N-Heterocyclic carbenes: application of ruthenium- alkylidene complexes in ring-opening metathesis polymerization [J]. J.Organomet. Chem., 1999,586:263-265.
63.T.Weskamp,W.A.Herrmann.Highly Active Ruthenium Catalysts for Olefin M-etathesis: T he Synergy of N-Heterocyclic Carbenes and Coordinatively Labile Ligands [J]. Angew.Chem.Int.Ed.,1999,38:2416-2419.
64.L.Ackermann,W.A.Herrmann.Ruthenium carbene complexes with imidazolin-2-ylidene ligands allow the formation of tetrasubstituted cycloalkenes by RCM [J].Tetra.Lett., 1999,40:4787-4790.
65.T.M.Trnka,R.H.Gubbs.The Development of L2X2Ru=CHR Olefin Metathesis Catalysts: An Organometallic Success Story [J]. Acc.Chem.Res.,2001,34:18-29.
66.A.Furstner.Olefin Metathesis and Beyond [J].Angew.Chem.Int.Ed.,2000,39: 3012-3033.
67.A.Furstner,L.Ackermann.Comparative Investigation of Ruthenium-Based Metathesis Catalysts Bearing N-Heterocyclic Carbene (NHC) Ligands [J]. Chem.Eur.J.,2001,7:3236-3253.
68.M.Scholl,R.H.Grubbs. Increased Ring Closing Metathesis Activity of Rutheni-um-Based Olefin Metathesis Catalysts Coordinated with Imidazolin-2-ylidene Ligands [J]. Tetra.Lett., 1999,40:2247-2250.
69. J.Huang,S.P.Nolan.Influence of Sterically Demanding Carbene Ligation on Cata-lytic Beh avior and Thermal Stability of Ruthenium Olefin Metathesis Catalysts [J]. Organometalli cs,1999,18:5375-5380.
70.R.H.Grubbs,M.J.Marsella.Template-directed ring-closing metathesis and ring-open-ing met athesis polymerization of functionalized dienes [P]. WO 98/30557,1998;WO 00/071554,2000.
71.R.H.Grubbs,T.M.Trnka.Novel Ruthium metal alkylidene complexes coordinate-ed with triazolylidene ligands that exhibit high olefin metathesis activity [P]. WO 00/058322,2000.
72.C.S.Woodson,R.H.Grubbs.Method for extending the pot life of an olefin me-tathesis polymerization reaction [P]. US 5939504,2000.
73.M.School,R.H.Grubbs.Synthesis and Activity of a New Generation of Ruthenium-Based Olefin Metathesis Catalysts Coordinated with 1,3-Dimesityl-4,5-di-hydroim-idazol-2-ylidene Ligands[J]. Org.Lett., 1999,1:953-956.
74.C.W.Bielawski,R.H.Grubbs.Highly Efficient Ring-Opening Metathesis Polyme-rization (ROMP) Using New Ruthenium Catalysts Containing N-Heterocyclic Carbene Ligands [J]. Angew.Chem.Int.Ed.,2000,39:2903-2905.
75.L.Jafarpour,S.P.Nolan. (p-cymene)RuLCl2 (L =1,3-Bis(2,4,6-trimethylphenyl) im-idazol-2-ylidene and 1,3-Bis(2,6-diisopropylphenyl)imidazol-2-ylidene) and RelatedComplexes as Ring Closing Metathesis Catalysts,[J].Organometallics, 1999,18:3760-3763.
76.T.L.Choi,R.H.Grubbs.Synthesis of α,β-Unsaturated Amides by Olefin Cross-Metathesis[J].Angew.Chem.Int.Ed.,2001,40:1277-1279.
77.A.Furstner,S.P.Nolan.Ruthenium Carbene Complexes with N,N'-Brs(mesityl) imidazol-2-ylidene Ligands: RCM Catalysts of Extended Scope [J].J.Org.Chem., 2000,65:2204-2209.
78.L.Jafarpour,S.P.Nolan. Development of olefin metathesis catalyst precursors bearing nucleophilic carbene ligands [J].J.Organomet.Chem.,2001,617:17-27.
79.J.Louie,R.H.Grubbs.Highly Active Metathesis Catalysts Generated In Situ fro-m Inexpens ive and Air-Stable Precursors[J].Angew.Chem.Int.Ed.,2001,40:247-251.
80.A.Furstner,H.Krause.Practical Method for the Rhodium-Catalyzed Addition of Aryl- and Alkenylboronic Acids to Aldehydes[J].Adv.Synth.Catal.,2001,343:343-350.
81.C.Moreau,C.G.Frost,Rhodium-catalysed aryl transfer to aldehydes:counterion effects with nitrogen containing ligands[J],Tetra.Lett.,2001,42:6957-6960.
82.A.O.Larsen,C.N.Oberhuber.Bidentate NHC-Based Chiral Ligands for Efficient Cu-Catalyzed Enantioselective Allylic Alkylations:Structure and Activity of An Air-Stable Chiral Cu Complex[J].J.Am.Chem.Soc.,2004,126:11130-11131.
83.J.Pytkowicz,P.Mangeney,Enantioselective conjugate addition of diethylzinc Using catalytic silver(Ⅰ)diaminocarbenes and Cu(OTf)[J].Tetrahedron:Asym-metry,2001,12:2087-2089.
84.H.M.Lee,S.P.Nolan,Catalytic Hydrogenation of Alkenes by the Ruthenium-Carbene Complex HRu(CO)CI(PCy3)(IMes)(IMes=Bis(1,3-(2,4,6-trimethyl phenyl)imidazol-2-ylidene)[J].Organometallics,2001,20:794-797,
85.C.Bolm,T.Focken.Synthesis of iridium complexes with novel planar chiral chelating imidazolylidene ligands[J],Tetrahedron:Asymmetry,2003,14:1733-1746.
86.M.C.Perry,K.Burgess,Optically Active Iridium Imidazol-2-ylidene-oxazoline Complexes:Preparation and Use in Asymmetric Hydrogenation of Arylalken-es[J],J.A m.Chem.Soc.,2003,125:113-123.
87.B.Cetinkaya,P.H.Dixneuf.Synthesis and catalytic properties of N-functionalized carbene complexes of rhodium(Ⅰ)and ruthenium(Ⅱ)[J],J.Organomet.Chem.,1997,534:153-158.
88.M.R.Fructos,S.P.Nolan,Complete Control of the Chemoselectivity in Catalyt-ic Carbene Transfer Reactions from Ethyl Diazoacetate:An N-Heterocyclic Carbene-Cu System That Suppresses Diazo Coupling[J],J.Am.Chem.Soc.,2004,126:10846-10847.
89.M.B.Andrus,J.Liu,Synthesis of resveratrol using a direct decarbonylative He-ck approac h from resorcylic acid [J]. Tetra.Lett.,2003,44:4819-4822.
90.C.Desmarets,Y.Fort. Nickel(0)/Imidazolium Chloride Catalyzed Reduction of Ar-yl Halides [J]. Organometallics,2002,21:1554-1559.
91.R.Singh,S.P.Nolan. Transesterification/Acylation of Secondary Alcohols Medi-ated by N-Heterocyclic Carbene Catalysts [J]. J.Org.Chem.,2004,69:209-212.
92.J.A.Mueller,M.S.Sigman. Elucidating the Significance of β-Hydride Eliminati-on and the Dynamic Role of Acid/Base Chemistry in a Palladium- CatalyzedAerobic Oxidation of Alcohols [J]. J.Am.Chem.Soc.,2004,126:9724- 9734.
93.M.Muehlhofer,W.A.Herrmann.New Catalyst Systems for the Catalytic Conver-sion of Methane into Methanol [J]. Angew.Chem.Int.Ed.,2002,41:1745-1747.
94.S.Lee,J.F.Hartwig.Improved Catalysts for the Palladium-Catalyzed Synthesis Of Oxindoles by Amide -Arylation. Rate Acceleration, Use of Aryl Chloride Subst-rates,and a New Carbene Ligand for Asymmetric Transformations [J]. J.Org.Chem., 2001,66:3402-3415.
95.Y.Chen,O.Meth-Cohn.Heterocycles Derived from Heteroatom-Substituted Car-benes [J]. Chem.Rev.,2004,104:2507-2530.
96.D.Enders,T.Balensiefer.Nucleophilic Carbenes in Asymmetric Organo-catalysis[J].Acc.Chem.Res.,2004,37:534-541.
97.(a) V. Prelog and G. Helmchen..Basic Principles of the CIP-System and Pr-opo-sals for a Revision [J]. Angew. Chem., Int. Ed. Engl., 1982,21:567-583.
98.D. S. Masterson, T. L. Hobbs and D. T. Glatzhofer. Cyclophanes as Templ-ates in Stereoselective SynthesisJ [J]. Mol. Cat. A:Chem., 1999, 145: 75-79.
99.C. Bolm and T. Kuhn, These results suggested that several, structural featu-res of the hydroxamic acid significantly, Synlett, 2000, 6: 899-901.
100.Y. Belokon, M. Moscalenko, N. Ikonnikov, L. Yashkina,D. Antonov, E. Voront sov and V. Rozenberg. Asymmetric trimethylsilylcyanation of benzal-dehyde catalyzed by (salen)Ti(IV) complexes derived from (R)- and/or (S)-4-hydroxy-5-formyl[2.2]paracyclophane and diamines[J]. Tetrahedron:Asymmetry,1997, 8:3245-3250.
101.S. Dahmen and S. BrSse. [2.2]Paracyclophane-Based N,O-Ligands in Alken-ylzinc Additions to Aldehydes[J].Org. Lett., 2001, 25: 4119-4122.
102.V.I,Rozenberg,D,Y,Antonov,R,P,Zhuravsky,E,V,Vorontsov,V,N.Khrustalev,N,S,Ikonnikov and Y,N,Belokon,Elaboration of a novel type of planarchiral methylene bridged biphenois based on[2.2]paracyclophanes[J],Tetr- a hedron:Asym metry,2000,11:2683-2693.
103.X,-L,Hou,X,-W,Wu,L,-X,Dai,B,-X,Cao and J,Sun,Novel N,S- and N,Se-PI anar Chiral[2.2]Paracyclophane Ligands:Synthesis and application in Pal-Catalyzed Allylic[J],Alkylation Chem.Commun.,2000,1195.
104.X,-W,Wu,X,-L,Hou,L,-X,Dai,J,Tao,B,-X,Cao and J,Sun,Syn-thesis of N ovel N,O-Planar Chiral[2.2]Paracyclophan Ligands and Their Ap-plication in Addition o f Diethylzinc to Aldehydes[J].Tetrahedron:Asymmetry,2001,12:529-531.
105.P.J,Pye,K,Rossen,R,A,Reamer,R,P,Volante and P,J,Reider.[2.2]PHANEPHOS-Ruthenium(Ⅱ)complexes:Highly active asymmetric catalysts for t-he hy drogenation of β-ketoesters[J],Tetrahedron Lett.,1998,39:4441-4444.
106.P.J,Pye,K,Rossen,R,A,Reamer,N,N,Tsou,R,P,Volante andP,J.Reider,A New Planar Chiral Bisphosphine Ligand for Asymmetric Catalysis:Highly En antioselective Hydrogenations under Mild Conditions[J],J.Am.Chem,Soc.,1997,119:6207-6208.
107.K,Rossen,P,J,Pye,A,Maliakal and R,P,Volante,Kinetic Resolution Of rac-4,12-Dibromo[2.2]paracyclophane in a Palladium[2.2]PHANEPHOS Catalyze-d Amination[J].J,Org,Chem.,1997:6462-6463.
108.周彤,山东大学硕士毕业论文,2006,7
109.房玺,山东大学硕士毕业论文,2007,7
110.王振军,董发昕.[2.2]对环二苯的合成[J].有机化学,2001,21:538-540.
111.PJ Ball,Tanya Rarog Shtoyko,Jeanette A,Krause Bauer,Warren J.Oidham,and Wiilia m B.Connick.Binuclear Rhenium(Ⅰ)Complexes with Bridging[2.2]Paracycl-ophane-Diimin e Ligands:Probing Electronic Coupling through π-πInteractions[J],Inorg,Chem.,2004A3:622-625.
112.D.Christopher Braddock,Simon M.Ahmad,A preparative microwave metho-d for isome risation of 4,16-dibromo[2.2]paracyclophane into 4,12-dibromo[2.2]paracyclophane[J].Tetra hedron Lett.,2004,45:6583-6588.
113.Valeria Rozenberg,Roman Zhuravsky,and Elena Sergeeva. Design,Classificat-ion,and stra tegies of Synthesis of Modular Bidentate Ligands Based on Aryl[2.2]paracyclophane Bac kbone[J].CHIRALITY,2006,18; 95-99.
114.Daniel T.Glatzhofer, Raymond R.Roy,and Kimberly N.Cossey. Conversion Of N-Aromatic Amides to O-Aromatic Esters [J].Org.Lett.,2002,4:2349-2351.
115. Jon C.Antilla,Artis Klapars, and Stephen L. Buchwald.The Copper-Catalyzed N-Arylation of Indoles[J]. J. Am. Chem. Soc.,2002,124:39-41.
2,A,J,Arduengo,A stable crystalline carbene[J],J,Am,Chem Soc.,1991,113:361-363.
3,W.A,Herrmann,N-Heterocyclic Carbenes:A New Concept in Organometall-ic Catalysis [J],Angew,Chem,Int,Ed.,2002,41:1290-1309.
4,D,J,Cram,Cyclophane chemistry:bent and battered benzene rings[J].Acc.Chem,Res.,1971,4:204-238.
5,E.L,Popova,V.I,Rozenberg,Z.A,Staikova,H,Hopf,Thermotropic Liquid Crystals from Planar Chiral Compounds:Optically Active Mesogenic[2.2]Par-acyclophan e Derivatives[J],Angew,Chem,Int,Ed.,2002,41:3411-3414.
6,J,Lahann,H,Hocker,R,Langer,Synthesis of Amino[2.2]paracyclophanes-Beneficial Monomers for Bioactive Coating of Medical Implant Materials[J].Angew,Chem,Int,Ed.,2001,40:726-278.
7,S,E,Gibson,J,D,Knight,[2.2]Paracyclophane derivatives in asymmetric catalysis[J],Org,Biomol,Chem.,2003,1:1256-1269.
8,P.J,Dyson,B.F.G,Johnson,C.M,Martin,Ruthenium cluster-[2.2]paracyclophan-e compl exes[J],Coord,Chem,Rev.,1998,175:59-89.
9.A.J.Arduengo,Preparation of 1,3-disubstituted imidazolium salts[P].US,1991,5077414.
10.A.A.Gridnev,I.M.Mihalteseva,Synthesis of l-Alkylimidazoles[J],Syn.Com-mun.,1994,24:1547-1555.
11.A.J.Arduengo,IIIR.Krafczyk,Imidazolylidenes,Imidazolinylidenes and lmid-azo-lidines [J],Tetrahedron,1999,55:14523-14534.
12.F.E.Hahn,L.Wittenbecher,Evidence for an Equilibrium between an N-heter-ocyclic Carb ene and Its Dimer in Solution[J],Angew.Chem.Int.Ed.,2000,39:541-543.
13.D.Enders,K.Breuer,Preparation,Structure,and Reactivity of 1,3,4-Triphenyl-4,5-dihydrolH-1,2,4-triazol-5-ylidene,a New Stable Carbene[J],Angew.Chem.Int.Ed.,1995,34:1021- 1023.
14.D.Ender,K.Breuer,1,3,4-Tdphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene appl-ications of a stable earbene in synthesis and catalysis[J],J,Prakt.Chem.,1997,339:397-399.
15.W.A,Herrmann,N-Heterocyclic Carbenes:A New Concept in Organometalli-c Catalysis [J].Angew.Chem.Int.Ed.,2002,41:1290-1309.
16.W.A.Herrmann,K.Ofele,Oxy Functionalization of Metal-Coordinated Hetero-cyclic Carb enes[J].Organometallics,1995,14:1085-1086.
17.W.A.Herrmann,C.Koeher,N-Heterocyelic Carbene Complexes of Palladium:Well-Defined,Air-Stable,Recyclable Catalysts for the Heck Reaction[J].Chem.Eur.J.,1996,2:772-779.
18.W.Baratta,W.A.Herrmann,Convenient syntheses of novel ruthenium catalysts bearing N-heterocyclic carbenes[J].J.Organomet.Chem.,2000,593:489-493.
19.K.Ofele,W.A.Herrmann,Metal complexes of acyclic diaminocarbenes:links between N-heterocyclic carbene(NHC)and Fischer-carbene complexes[J].J.Organomet.Chem.,2003,684:235-248.
20.I.Huang,S.P.Nolan,Stereoelectronic Effects Characterizing Nucleophilic Carb-ene Ligands Bound to the Cp~*RuCI(Cp~*= 5-C5Me5)Moiety:A Structural And Thermochemical Investigation[J].Organometallics,1999,18:2370-2375.
21.W.A.Herrmann,O.Runte,Synthesis and structure of an ionic beryllium- "car-bene" com plex[J],J.Organomet.Chem.,1995,501:C1-C4.
22.H.Schumann,J.Gottfriedsen,Metallocenes of the alkaline earth metals and t-heir carbene complexes[J],J.Organomet.Chem.,2001,617:588-600.
23.M.H.Voges,C.Romming.Synthesis and Characterization of 14-Electron Cyciop-entadienyi Chromium(Ⅱ)Complexes Containing a Heterocyclic Carbene Liga-nd[J].Organometallics,1999,18:529-533.
24.C.D.Abernathy,A.H.Cowley,Reaction of nickelocene with 1,3-dimesityl imid-azolium chl oride[J],J.Organomet.Chem.,2000,596:3.5.
25.J.C.Garrison,W.J.Youngs,Synthesis and Structural Characterization of an Imi-dazolium-Li nked Cyelophane and the Silver Complex of an N-Heterocyclic Carbene-Linked Cyclophane[J].Organometallics,2001,20:1276-1278.
26.J.Pytkowicz,S.Roland.Synthesis of Chiral silver(I) diaminocarbene complexes from (R,R)-4,5-di-tert-butylimidazoline [J].J.Organomet.Chem.,2001,631:157- 163.
27.R.A.Batey,M.Shen. Carbamoyl-Substituted N-Heterocyclic Carbene Complexes of Palladium(II): Application to Sonogashira Cross-Coupling Reactions [J]. Org. Lett, 2002,4:1411-1414.
28.W.A.Herrmann, M.Elison. Metal Complexes of N-Heterocyclic Carbenes-A New Structural Principle for Catalysts in Homogeneous Catalysis [J]. Angew. Chem. Int.Ed., 1995,34:2371-2374.
29.C.Yang, S.P.Nolan. Highly Efficient Heck Reactions of Aryl Bromides with n-Butyl Ac rylate Mediated by a Palladium/Phosphine-Imidazolium Salt Syste-m[J].Org.Lett.,2001,3:1511-1514.
30.M.B.Andrus,C.Song. Palladium-Imidazolium Carbene Catalyzed Mizoroki-Hec-k Coupling with Aryl Diazonium Ions [J]. Org.Lett.,2002,4:2079-2082.
31 J.A.Loch,R.H.Crabtree,.Palladium Complexes with Tridentate Pincer Bis-Carb-ene Ligands as Efficient Catalysts for C-C Coupling,[J]. Organometallics, 2002,21:700-706.
32.M.B.Andrus,J.Liu. Synthesis of resveratrol using a direct decarbonylative He-ck approac h from resorcylic acid[J].Tetra.Lett.,2003,44:4819-4822.
33.M.Mayr,M.R.Buchmeiser.1,3-Dialkyl- and 1,3-Diaryl-3,4,5,6-tetrahydro pyrimi-in-2-ylidene Rhodium(i) and Palladium(II) Complexes: Synthesis, Structure,and Reactivity [J].Chem.Eur.J.,2004,10:1256-1266.
34.K.Selvakumar, M.Beller.Synthesis of Monocarbenepalladium(0)Complexes and Their Catalytic Behavior in Cross-Coupling Reactions of Aryldiazonium Salts[J]. Chem.Eur.J.,2002,8:3901-3906.
35. C.W.K.Gstottmayr,W.A.Herrmann.A Defined N-Heterocyclic Carbene Compl-ex for the Palladium-Catalyzed Suzuki Cross-Coupling of Aryl Chlorides at Ambient Temperatures[J].Angew.Chem.Int.Ed.,2002,41:1363-1365.
36.G.Altenhoff,F.Glorius, Sterically Demanding. Bioxazoline-Derived N-Heterocy-clic Carbene Ligands with Restricted Flexibility for Catalysis [J]. J.Am.Chem.Soc.,2004,126:15195-1 52001.
37.A.Furstner,A.Leitner.General and User-friendly Method for Suzuki Reactions with Aryl Chlorides[J].Synlett.,2001,2:290-292.
38.O.Navatro,S.P.Nolan,Cross-Coupling and Dehalogenation Reactions Catalyzed By(N-H eterocyclic carbene)Pd(allyl)Cl Complexes[J],J.Org.Chem.,2004,69:3173-3180.
39.O.Navarro,S.P.Nolan,A General Method for the Suzuki-Miyaura Cross-Coup-ling of Ster ically Hindered Aryl Chlorides:Synthesis of Di-and Tri-orthosu-bstituted Biaryls in 2-P ropanol at Room Temperature[J],J.Am.Chem.Soc.,2003,125:16194-16195.
40.M.B.Andrus,C.Song,Palladium-Imidazolium Carbene Catalyzed Aryl,Vinyl,And Alkyl Suzuki-Miyaura Cross Coupling[J],Org.Lett.,2001,3:3761-3764.
41.H.M.Lee,S.P.Nolan.Efficient Cross-Coupling Reactions of Aryl Chlorides and Bromides with Phenyl- or Vinyltrimethoxysilane Mediated by a Palladium/Imidazolium Chloride System[J].Org.Lett.,2000,2:2053-2055.
42.E.Peris,J.A.Loch,Palladium Complexes with Tridentate Pincer bis-Carbene Ligands as Efficient Catalysts for C-C Coupling[J].Chem.Commun.,2001,23:201-204.
43.V.P.W.Bohm,W.A.Herrmann.Nickel-Catalyzed Cross-Coupling of Aryl Chlori-des with Ar yl Grignard Reagents[J].Angew.Chem.Int.Ed.,2000,39:1602-1604.
44.S.Caddick,M.R.V.Williams.An improved synthesis of bis(1,3-di-N-tertbutylimi-dazol-2-ylid ene)palladium(0)and its use in C-C and C-N coupling reactions[J],J.Organomet.Chem.,2001,617:635-639.
45.O.A.Grasa,S.P.Nolan.Palladium/Imidazolium Salt Catalyzed Coupling of Aryl Halides with Hypervalent Organostannates[J],Org.Lett.,2001,3:119-122.
46.A.C.Hillier,S.P.Nolan.Catalytic cross-coupling reactions mediated by palladium/nucleophili c carbene systems[J],J.Organomet.Chem.,2002,653:69-82.
47.P.Espinet,A.M.Echavarren,The Mechanisms of the Stille Reaction[J].Angew.Chem.Int.Ed.,2004,43:4704-4734
48.A.K.Lewis,S.Caddic.Synthetic,Structural,and Mechanistic Studies on the Ox-idative Add ition of Aromatic Chlorides to a Palladium(N-Heterocyclic Carbe-ne)Complex:Relevanc e to Catalytic Amination[J],J.Am.Chem.Soc.,2003,125:10066-10073.
49.J.Huang,S.P.Nolan.General and Efficient Catalytic Amination of Aryl Chlori-des Using a Palladium/Bulky Nucleophilic Carbene System[J],Org.Lett.,1999,1:1307-1309.
50.M.S.Viciu,S.P.Nolan.An Air-Stable Palladium/N-Heterocyclic Carbene Compi-ex and Its Reactivity in Aryl Amination[J].Org.Lett.,2002,4:2229-2231.
51.M.S.Viciu,S.P.Nolan.Synthesis,Characterization,and Catalytic Activity of N-Heterocyclic Carbene(NHC)Palladacycle Complexes[J],Org.Lett.,2003,5:1479-1482.
52.M.S.Viciu,S.P.Nolan.Activation and Reactivity of(NHC)Pd(allyl)Cl(NHC=N-Heterocyclic Carbene)Complexes in Cross-Coupling Reactions[J],Organome-tallics,2002,21:5470-5472.
53.G.A.Grasa,S.P.Nolan.Amination Reactions of Aryl Halides with Nitrogen-Contai-ning Rea gents Mediated by Palladium/Imidazolium Salt Systems[J],J.Org.Chem.,2001,66:7729-7737.
54.S.R.Stauffer,J.F.Hartwig,High Turnover Number and Rapid,Room-Temperat-ure Aminati on of Chloroarenes Using Saturated Carbene Ligands[J].Org.Lett.,2000,2:1423-1426.
55.J.Cheng,M.L.Trudell.Synthesis of N-Heteroaryl-7-azabicyclo[2.2.1]heptane Der-ivatives via Palladium-Bisimidazol-2-ylidene Complex Catalyzed Amination Reactions[J],Org.Lett.,2001,3:1371-1374.
56.B.Gradel,Y.Fort.Nickel-catalysed amination of aryl chlorides using a dihydro-imidazoline carbene ligand[J],Tetra.Lett.,2001,42:5689-5692.
57.C.Desmarets,Y.Fort.Nickel(0)/Dihydroimidazol-2-ylidene Complex Catalyzed Coupling of Aryl Chlorides and Amines[J].J.Org.Chem.,2002,67:3029-3036.
58.a).W.A.Herrmann,J.Schwarz,High-Yield Syntheses of Sterically Demanding Bis-(N-hetero cyclic carbene)Complexes of Palladium[J],Organometallics,1999,18:4082-4089.
b).T.Weskamp,W.A.Herrmann.Combining N-heterocyclic carbenes and phosphines:improve d palladium(Ⅱ)catalysts for aryl coupling reactions[J].J.Organomet.Chem.,1999,585:348-352. c).W.A.Herrmann, J.Schwarz.Homoleptic chelating N-heterocyclic carbine comple-xes of palla dium and nickel [J].J.Organomet.Chem.,1999,575:80-86.
d).V.P.W.Bohm,W.A.Herrmann.N-Heterocyclic carbenes: Part 26. N-Heterocyclic carbene complexes of palladium(0): synthesis and application in the Suzuki cross-coupling reaction [J]. J.Organomet.Chem.,2000,595:186-190.
59.W.A.Herrmann,V.P.W.Bohm.Synthesis, structure and catalytic application of palladium(II) complexes bearing N-heterocyclic carbenes and phosphines [J].J. Organomet. Chem.,2001,617:616-628.
60.T.Weskamp,W.A.Herrmann, A Novel Class of Ruthenium Catalysts for Olef-in Metathes is [J].Angew.Chem.Int.Ed.,1998,37:2490-2493.
61.T.Weskamp,W.A.Herrmann, N-heterocyclic carbenes: novel ruthenium-alkylid-ene complexes,[J]. J.Organomet.Chem.,1999,582,362-365.
62.U.Frenzel,W.A.Herrmann.N-Heterocyclic carbenes: application of ruthenium- alkylidene complexes in ring-opening metathesis polymerization [J]. J.Organomet. Chem., 1999,586:263-265.
63.T.Weskamp,W.A.Herrmann.Highly Active Ruthenium Catalysts for Olefin M-etathesis: T he Synergy of N-Heterocyclic Carbenes and Coordinatively Labile Ligands [J]. Angew.Chem.Int.Ed.,1999,38:2416-2419.
64.L.Ackermann,W.A.Herrmann.Ruthenium carbene complexes with imidazolin-2-ylidene ligands allow the formation of tetrasubstituted cycloalkenes by RCM [J].Tetra.Lett., 1999,40:4787-4790.
65.T.M.Trnka,R.H.Gubbs.The Development of L2X2Ru=CHR Olefin Metathesis Catalysts: An Organometallic Success Story [J]. Acc.Chem.Res.,2001,34:18-29.
66.A.Furstner.Olefin Metathesis and Beyond [J].Angew.Chem.Int.Ed.,2000,39: 3012-3033.
67.A.Furstner,L.Ackermann.Comparative Investigation of Ruthenium-Based Metathesis Catalysts Bearing N-Heterocyclic Carbene (NHC) Ligands [J]. Chem.Eur.J.,2001,7:3236-3253.
68.M.Scholl,R.H.Grubbs. Increased Ring Closing Metathesis Activity of Rutheni-um-Based Olefin Metathesis Catalysts Coordinated with Imidazolin-2-ylidene Ligands [J]. Tetra.Lett., 1999,40:2247-2250.
69. J.Huang,S.P.Nolan.Influence of Sterically Demanding Carbene Ligation on Cata-lytic Beh avior and Thermal Stability of Ruthenium Olefin Metathesis Catalysts [J]. Organometalli cs,1999,18:5375-5380.
70.R.H.Grubbs,M.J.Marsella.Template-directed ring-closing metathesis and ring-open-ing met athesis polymerization of functionalized dienes [P]. WO 98/30557,1998;WO 00/071554,2000.
71.R.H.Grubbs,T.M.Trnka.Novel Ruthium metal alkylidene complexes coordinate-ed with triazolylidene ligands that exhibit high olefin metathesis activity [P]. WO 00/058322,2000.
72.C.S.Woodson,R.H.Grubbs.Method for extending the pot life of an olefin me-tathesis polymerization reaction [P]. US 5939504,2000.
73.M.School,R.H.Grubbs.Synthesis and Activity of a New Generation of Ruthenium-Based Olefin Metathesis Catalysts Coordinated with 1,3-Dimesityl-4,5-di-hydroim-idazol-2-ylidene Ligands[J]. Org.Lett., 1999,1:953-956.
74.C.W.Bielawski,R.H.Grubbs.Highly Efficient Ring-Opening Metathesis Polyme-rization (ROMP) Using New Ruthenium Catalysts Containing N-Heterocyclic Carbene Ligands [J]. Angew.Chem.Int.Ed.,2000,39:2903-2905.
75.L.Jafarpour,S.P.Nolan. (p-cymene)RuLCl2 (L =1,3-Bis(2,4,6-trimethylphenyl) im-idazol-2-ylidene and 1,3-Bis(2,6-diisopropylphenyl)imidazol-2-ylidene) and RelatedComplexes as Ring Closing Metathesis Catalysts,[J].Organometallics, 1999,18:3760-3763.
76.T.L.Choi,R.H.Grubbs.Synthesis of α,β-Unsaturated Amides by Olefin Cross-Metathesis[J].Angew.Chem.Int.Ed.,2001,40:1277-1279.
77.A.Furstner,S.P.Nolan.Ruthenium Carbene Complexes with N,N'-Brs(mesityl) imidazol-2-ylidene Ligands: RCM Catalysts of Extended Scope [J].J.Org.Chem., 2000,65:2204-2209.
78.L.Jafarpour,S.P.Nolan. Development of olefin metathesis catalyst precursors bearing nucleophilic carbene ligands [J].J.Organomet.Chem.,2001,617:17-27.
79.J.Louie,R.H.Grubbs.Highly Active Metathesis Catalysts Generated In Situ fro-m Inexpens ive and Air-Stable Precursors[J].Angew.Chem.Int.Ed.,2001,40:247-251.
80.A.Furstner,H.Krause.Practical Method for the Rhodium-Catalyzed Addition of Aryl- and Alkenylboronic Acids to Aldehydes[J].Adv.Synth.Catal.,2001,343:343-350.
81.C.Moreau,C.G.Frost,Rhodium-catalysed aryl transfer to aldehydes:counterion effects with nitrogen containing ligands[J],Tetra.Lett.,2001,42:6957-6960.
82.A.O.Larsen,C.N.Oberhuber.Bidentate NHC-Based Chiral Ligands for Efficient Cu-Catalyzed Enantioselective Allylic Alkylations:Structure and Activity of An Air-Stable Chiral Cu Complex[J].J.Am.Chem.Soc.,2004,126:11130-11131.
83.J.Pytkowicz,P.Mangeney,Enantioselective conjugate addition of diethylzinc Using catalytic silver(Ⅰ)diaminocarbenes and Cu(OTf)[J].Tetrahedron:Asym-metry,2001,12:2087-2089.
84.H.M.Lee,S.P.Nolan,Catalytic Hydrogenation of Alkenes by the Ruthenium-Carbene Complex HRu(CO)CI(PCy3)(IMes)(IMes=Bis(1,3-(2,4,6-trimethyl phenyl)imidazol-2-ylidene)[J].Organometallics,2001,20:794-797,
85.C.Bolm,T.Focken.Synthesis of iridium complexes with novel planar chiral chelating imidazolylidene ligands[J],Tetrahedron:Asymmetry,2003,14:1733-1746.
86.M.C.Perry,K.Burgess,Optically Active Iridium Imidazol-2-ylidene-oxazoline Complexes:Preparation and Use in Asymmetric Hydrogenation of Arylalken-es[J],J.A m.Chem.Soc.,2003,125:113-123.
87.B.Cetinkaya,P.H.Dixneuf.Synthesis and catalytic properties of N-functionalized carbene complexes of rhodium(Ⅰ)and ruthenium(Ⅱ)[J],J.Organomet.Chem.,1997,534:153-158.
88.M.R.Fructos,S.P.Nolan,Complete Control of the Chemoselectivity in Catalyt-ic Carbene Transfer Reactions from Ethyl Diazoacetate:An N-Heterocyclic Carbene-Cu System That Suppresses Diazo Coupling[J],J.Am.Chem.Soc.,2004,126:10846-10847.
89.M.B.Andrus,J.Liu,Synthesis of resveratrol using a direct decarbonylative He-ck approac h from resorcylic acid [J]. Tetra.Lett.,2003,44:4819-4822.
90.C.Desmarets,Y.Fort. Nickel(0)/Imidazolium Chloride Catalyzed Reduction of Ar-yl Halides [J]. Organometallics,2002,21:1554-1559.
91.R.Singh,S.P.Nolan. Transesterification/Acylation of Secondary Alcohols Medi-ated by N-Heterocyclic Carbene Catalysts [J]. J.Org.Chem.,2004,69:209-212.
92.J.A.Mueller,M.S.Sigman. Elucidating the Significance of β-Hydride Eliminati-on and the Dynamic Role of Acid/Base Chemistry in a Palladium- CatalyzedAerobic Oxidation of Alcohols [J]. J.Am.Chem.Soc.,2004,126:9724- 9734.
93.M.Muehlhofer,W.A.Herrmann.New Catalyst Systems for the Catalytic Conver-sion of Methane into Methanol [J]. Angew.Chem.Int.Ed.,2002,41:1745-1747.
94.S.Lee,J.F.Hartwig.Improved Catalysts for the Palladium-Catalyzed Synthesis Of Oxindoles by Amide -Arylation. Rate Acceleration, Use of Aryl Chloride Subst-rates,and a New Carbene Ligand for Asymmetric Transformations [J]. J.Org.Chem., 2001,66:3402-3415.
95.Y.Chen,O.Meth-Cohn.Heterocycles Derived from Heteroatom-Substituted Car-benes [J]. Chem.Rev.,2004,104:2507-2530.
96.D.Enders,T.Balensiefer.Nucleophilic Carbenes in Asymmetric Organo-catalysis[J].Acc.Chem.Res.,2004,37:534-541.
97.(a) V. Prelog and G. Helmchen..Basic Principles of the CIP-System and Pr-opo-sals for a Revision [J]. Angew. Chem., Int. Ed. Engl., 1982,21:567-583.
98.D. S. Masterson, T. L. Hobbs and D. T. Glatzhofer. Cyclophanes as Templ-ates in Stereoselective SynthesisJ [J]. Mol. Cat. A:Chem., 1999, 145: 75-79.
99.C. Bolm and T. Kuhn, These results suggested that several, structural featu-res of the hydroxamic acid significantly, Synlett, 2000, 6: 899-901.
100.Y. Belokon, M. Moscalenko, N. Ikonnikov, L. Yashkina,D. Antonov, E. Voront sov and V. Rozenberg. Asymmetric trimethylsilylcyanation of benzal-dehyde catalyzed by (salen)Ti(IV) complexes derived from (R)- and/or (S)-4-hydroxy-5-formyl[2.2]paracyclophane and diamines[J]. Tetrahedron:Asymmetry,1997, 8:3245-3250.
101.S. Dahmen and S. BrSse. [2.2]Paracyclophane-Based N,O-Ligands in Alken-ylzinc Additions to Aldehydes[J].Org. Lett., 2001, 25: 4119-4122.
102.V.I,Rozenberg,D,Y,Antonov,R,P,Zhuravsky,E,V,Vorontsov,V,N.Khrustalev,N,S,Ikonnikov and Y,N,Belokon,Elaboration of a novel type of planarchiral methylene bridged biphenois based on[2.2]paracyclophanes[J],Tetr- a hedron:Asym metry,2000,11:2683-2693.
103.X,-L,Hou,X,-W,Wu,L,-X,Dai,B,-X,Cao and J,Sun,Novel N,S- and N,Se-PI anar Chiral[2.2]Paracyclophane Ligands:Synthesis and application in Pal-Catalyzed Allylic[J],Alkylation Chem.Commun.,2000,1195.
104.X,-W,Wu,X,-L,Hou,L,-X,Dai,J,Tao,B,-X,Cao and J,Sun,Syn-thesis of N ovel N,O-Planar Chiral[2.2]Paracyclophan Ligands and Their Ap-plication in Addition o f Diethylzinc to Aldehydes[J].Tetrahedron:Asymmetry,2001,12:529-531.
105.P.J,Pye,K,Rossen,R,A,Reamer,R,P,Volante and P,J,Reider.[2.2]PHANEPHOS-Ruthenium(Ⅱ)complexes:Highly active asymmetric catalysts for t-he hy drogenation of β-ketoesters[J],Tetrahedron Lett.,1998,39:4441-4444.
106.P.J,Pye,K,Rossen,R,A,Reamer,N,N,Tsou,R,P,Volante andP,J.Reider,A New Planar Chiral Bisphosphine Ligand for Asymmetric Catalysis:Highly En antioselective Hydrogenations under Mild Conditions[J],J.Am.Chem,Soc.,1997,119:6207-6208.
107.K,Rossen,P,J,Pye,A,Maliakal and R,P,Volante,Kinetic Resolution Of rac-4,12-Dibromo[2.2]paracyclophane in a Palladium[2.2]PHANEPHOS Catalyze-d Amination[J].J,Org,Chem.,1997:6462-6463.
108.周彤,山东大学硕士毕业论文,2006,7
109.房玺,山东大学硕士毕业论文,2007,7
110.王振军,董发昕.[2.2]对环二苯的合成[J].有机化学,2001,21:538-540.
111.PJ Ball,Tanya Rarog Shtoyko,Jeanette A,Krause Bauer,Warren J.Oidham,and Wiilia m B.Connick.Binuclear Rhenium(Ⅰ)Complexes with Bridging[2.2]Paracycl-ophane-Diimin e Ligands:Probing Electronic Coupling through π-πInteractions[J],Inorg,Chem.,2004A3:622-625.
112.D.Christopher Braddock,Simon M.Ahmad,A preparative microwave metho-d for isome risation of 4,16-dibromo[2.2]paracyclophane into 4,12-dibromo[2.2]paracyclophane[J].Tetra hedron Lett.,2004,45:6583-6588.
113.Valeria Rozenberg,Roman Zhuravsky,and Elena Sergeeva. Design,Classificat-ion,and stra tegies of Synthesis of Modular Bidentate Ligands Based on Aryl[2.2]paracyclophane Bac kbone[J].CHIRALITY,2006,18; 95-99.
114.Daniel T.Glatzhofer, Raymond R.Roy,and Kimberly N.Cossey. Conversion Of N-Aromatic Amides to O-Aromatic Esters [J].Org.Lett.,2002,4:2349-2351.
115. Jon C.Antilla,Artis Klapars, and Stephen L. Buchwald.The Copper-Catalyzed N-Arylation of Indoles[J]. J. Am. Chem. Soc.,2002,124:39-41.