碳-碳、碳-氮键的构建研究.pdf

黪硇竹女I博士掌位论文史雷涂永强教授史雷中文摘要兰州大学功能有机分子化学国家重点实验室及化学系 2005年5月本论文完成了“碳—碳、碳一氮键的构建”的研究,其主要包括以下四个部分内容: 一、微波促进的无金属催化的芳基卤代物快速直接***化反应被发展。这个反应对富电子芳基卤代物的***化反应更为有效。在一些例子中,好的区域选择性被发现,这有利于从邻、对位取代的芳***制备间位取代的芳***。该反应经历一个苯炔中间体的过程。二、原位制备的RiekeNi促进的羰基化合物的频哪醇偶联反应被报道。同时, NiCl2(Cat)/Mg/TMSC催化体系被设计并成功地发展。这个反应是一个单电子反应机理,并且搋锄啪非对映选择性和添加剂效应被考察。三、微波促进的cui催化的醛、炔和***三组分偶联合成炔丙***的反应被发现。这个方法被证明对于很多底物都有效。而且,用∞-proline methyl ester作为手性源的三组分偶联合成炔丙***能够获得高的非对跌选择性。四、RhCI(PPh3)3(cat.)/BF3·OEt2( equiv.)/BuBr( equiv.)/toluene体系,促进的一级脂肪醇和芳基烯烃sp3-sp3 C—C键形成反应被首次报道,它为二级醇的合成提供了一条新的方法。一个自由基的反应机理被建议。≮≥漤词: 微波-无金属·***化反应-Rieke Ni·单电子转移·非对映选择性·三组分偶联·活化·氧化加成·Kharasch自由基反应黪硇埘虫掌博士学位论文史番 Tu LeiShi Abstract State KeyLab..Chem.&. Lanzhou University May2005 This thesis finishes Some studies towards“the Efficient Construetion of C—C or C-X bond”including mainly the following four parts rapid and direct amination ofaryl halides has been developed good to lligh yield under microwave irradiation without transition-metal method especially applicable to electron-rich arylhalides with various some cases,the excellent regioselectivity could be observed,which facilitated the preparation ofmeta-substituted anilines from ortho-orpara-substituted phenylhalides. Inaddition,a mechanism viathe interesting benzyne intermediate hasbeen proposed was firstly found thatthe Rieke Ni generated/n was abletopromote thepinacol coupling ofvarious carbonyls on this information, anothercatalytically effective,a cheaper and more convenient NiCl2(Cat.)/Mg/TMSCI system was designed and developed further interesting single—electron transfer(SET)mechanisms forthecoupling reactions were proposed. Additionally,the dl/meso diastereoseleetivity and some additive effects were also explained terms ofthe proposed mechanisms An ponentcoupling of aldehyde,alkyne,and amine to generate propargylamines hasbeeneffected under microwave irradiation water using only CuI catalyst without the nobl