过渡金属络合物的基本反应和催化机理PPT.pptVIP

卤代烃与格林亚试剂的偶联 Kumada偶联, M Kumada 和R J P Corriu, 1972 镍膦络合物催化下，卤代烯烃或卤代芳烃与格林亚试剂的偶联 改用钯膦络合物催化，可实现卤代烯烃或卤代芳烃与有机锂的偶联 Kumada偶联反应的特点 对于镍催化的偶联，配体的种类对活性有影响 Kumada偶联反应的特点（续） 有?氢的烷基格林亚试剂不会发生?氢消除 仲烷基格林亚试剂可能异构化，生成伯烷基产物 dppf为配体可加速?氢消除和还原消除，抑制仲烷基的异构化，可用于仲烷基格林亚试剂的偶联 卤代烯烃的构型保持 Heck反应的机理 由过渡金属络合物的一些基本反应构成，包括： 氧化加成（oxidative addition) 还原消除（reductive elimination) 转移金属化（transmetallation) 插入(insertion)和?氢消除(?-hydride elimination) Heck反应合成lasiodiplodin A potent anticancer macrocyclic natural product Fürstner, A., Thiel, O. R., Kindler, N., Bartkowska, B. Total Syntheses of (S)-(-)-Zearalenone and Lasiodiplodin Reveal Superior Metathesis Activity of Ruthenium Carbene Complexes with Imidazol-2-ylidene Ligands. J. Org. Chem. 2000, 65, 7990-7995 参考文献 卤代烃与炔烃的偶联 Castro-Stephens偶联 In the early 1960s, R.D. Stephens and C.E. Castro discovered that disubstituted acetylenes were produced in good yield upon treatment of aryl iodides with stoichiometric amounts of copper(I) acetylides under a nitrogen atmosphere in refluxing pyridine The copper(I) mediated coupling of aryl or vinyl halides with aryl- or alkyl-substituted alkynes is known as the Castro-Stephens coupling. Castro-Stephens偶联的机理 The reaction is believed to proceed via a four-centered transition state Castro-Stephens偶联的缺点 Most copper(I) salts are insoluble in organic solvents, so the reactions are often hetero-geneous and require high reaction temperatures The reactions are sensitive to functional groups on the aryl halides, and the yields are often irreproducible Castro-Stephens偶联合成tribenzocyclotriyne Kinder, J. D., Tessier, C. A., Youngs, W. J. Synthesis of a para-methoxy substituted tribenzocyclotriyne. Synlett 1993, 149-150 参考文献 Sonogashira偶联，1975 Catalytic version of the Castro-Stephens coupling Pd-catalyst: Pd(PPh3)2Cl2 or Pd(PPh3)4 Cu(I)-salt: CuI or CuBr base: Et2NH, Et3N, (i-Pr)2NEt solvent: MeCN, THF, EtOAc Sonogashira偶联的机理 Sonogashira偶联的特点 The coupling can usually be conducted at or slightly above room temperature The handli