【作者】 徐琴；

【导师】 施敏；

【作者基本信息】 华东理工大学 ， 应用化学， 2010， 博士

【摘要】 本论文主要围绕由联萘胺及H8-联萘胺衍生的氮杂环卡宾配体及其钯、铑金属络合物的合成,以及这些钯、铑金属络合物在催化反应中的应用来展开。主要由以下三部分工作组成。一.基于联萘胺和H8-联萘胺的轴手性氮杂环卡宾钯络合物的合成及其在芳基硼酸对N-取代-2,3-二氢-4-吡啶酮的不对称1,4-加成中的应用从H8-联萘胺出发合成了新型轴手性氮杂环卡宾金属钯络合物Ⅰ-10和Ⅰ-11,其结构得到NMR, EA, MS, IR以及X-ray单晶衍射确认。将络合物Ⅰ-1,Ⅰ-2,Ⅰ-3,Ⅰ-4,Ⅰ-10,Ⅰ-11应用于芳基硼酸对N-取代-2,3-二氢-4-吡啶酮的的不对称共轭加成,发现金属钯络合物Ⅰ-1,Ⅰ-10,Ⅰ-11无催化活性,而bis(NHC)-Pd(II)络合物Ⅰ-2,Ⅰ-3和Ⅰ-4可以高效催化芳基硼酸对N-取代-2,3-二氢-4-吡啶酮的不对称共轭加成,取得了高达96%的收率,>99.5%的ee值。二.基于联萘胺和H8-联萘胺的轴手性氮杂环卡宾铑络合物的合成及其在β-酮酯的不对称硅氢化反应中的应用从(R)-H8-联萘胺出发,合成了轴手性的氮杂环卡宾金属铑络合物Ⅱ-2。其结构经NMR,EA, MS, IR以及X-ray单晶衍射确认。并将金属铑络合物Ⅱ-1和Ⅱ-2应用于p-酮酯的不对称硅氢化反应,发现金属铑络合物Ⅱ-1和Ⅱ-2均具有优秀的不对称催化效果,取得了良好的收率和高达99%的ee值。三.基于联萘胺的轴手性氮杂环卡宾钯络合物在Suzuki和Heck-Mizoroki反应中的应用将双齿氮杂环卡宾金属钯络合物Ⅰ-1应用于催化Suzuki偶联反应,芳基溴化物和芳基碘化物分别与苯基硼酸的偶联取得了高达95%的收率；而且芳基氯化物与苯基硼酸的偶联也取得了中等的收率。同时,我们把双齿氮杂环卡宾金属钯络合物Ⅰ-1应用于催化Heck-Mizoroki偶联反应,也取得了高达99%的收率。更多还原

【Abstract】 This thesis mainly focused on the synthesis of axially chiral NHC-Rh(Ⅲ) and NHC-Pd(Ⅱ) complexes derived from BINAM and Hg-BINAM and applications of these complexes in the catalytic reactions. 1. An Efficient Asymmetric 1,4-Addition of Arylboronic Acids to 2,3-Dihydro-4-pyridones Catalyzed by Axially Chiral NHC-Pd (Ⅱ) Complexes.Novel axially chiral cis-chelated bidentate bis(N-heterocyclic carbene)-palladium(Ⅱ) complexesⅠ-10 andⅠ-11 derived from Hg-BINAM have been synthesized. Their structures have been characterized by X-ray diffraction of single crystals. Axially chiral NHC-Pd(Ⅱ) complexesⅠ-2,Ⅰ-3 andⅠ-4 are effective catalysts for the asymmetric conjugate addition of arylboronic acids to 2,3-dihydro-4-pyridones, producing the synthetically and biologically important 2-aryl-4-piperidones in moderate to high yields (up to 96%) and with excellent enantioselectivities (up to> 99.5%ee), in most cases under mild conditions. However, bis(NHC)-Pd(Ⅱ) complexesⅠ-1,Ⅰ-10 andⅠ-11 were ineffective in this reaction. 2. Synthesis of Novel Axially Chiral NHC-Rh(Ⅲ) Complexes Derived from BINAM and Hg-BINAM and Application in the Enantioselective Hydrosilylation of 3-Oxo-3-arylpropionic Acid Methyl or Ethyl Esters.Novel axially chiral cis-chelated bidentate bis(N-heterocyclic carbene)-Rhodium (Ⅲ) complexesⅡ-2 derived from Hg-BINAM have been synthesized. Their structures have been characterized by X-ray diffraction of single crystals. Axially chiral N-heterocyclic carbene (NHC)-Rh(Ⅲ) complexesⅡ-11 andⅡ-2 were applied in the enantioselective hydrosilylation of 3-oxo-3-arylpropionic acid methyl or ethyl esters. The reduction products, 3-hydroxy-3-arylpropionic acid methyl or ethyl esters, could be obtained in good yields (up to 90%) with good to excellent enantioselectivities (up to 99%ee) under mild conditions. 3. A Novel cis-Chelated Pd(Ⅱ)-NHC Complex for Catalyzing Suzuki and Heck-type Cross-coupling Reactions.Axially chiral cis-chelated bidentate bis(N-heterocyclic carbene)-palladium(Ⅱ) complexⅠ-1 is fairly effective in Suzuki cross-coupling reaction. Using either aryl bromides or iodobenzene as substrates afforded coupling products in 75-99%yields, moreover, using aryl chlorides afforded moderate yields of the coupling products. ComplexⅠ-1 was also effective in Heck-type cross-coupling reaction to give the corresponding products in good to excellent yields (up to 99%) in most cases.更多还原