【作者】 郭孟萍；

【导师】 何仁； 建方方；

【作者基本信息】 大连理工大学 ， 工业催化， 2006， 博士

【摘要】 在有机合成中,Suzuki交叉偶联反应是制备联苯类化合物最重要的方法之一,本论文设计并合成了二个P⌒O系列、一个P⌒N系列双齿配位的钯配合物。研究了它们对Suzuki偶联反应的催化作用,优化了这些催化剂在联苯类化合物合成中的反应条件。实验结果表明,这三个系列的配合物都是Suzuki偶联反应优良的催化剂,具有反应条件温和（室温）,催化活性高,选择性好,底物范围广等特点,具有潜在的工业应用前景。 1.改进了P⌒O双齿配体的合成方法。新方法反应条件温和、操作简单、产率高、产物纯度好。合成了三个P⌒O双齿螯合钯配合物:cis-Pd（Ph₂PCH₂COO）₂（40）、cisPd（Ph₂PCH₂CH₂COO）₂（41）和cis-Pd（o-Ph₂PC₆H₄COO）₂（42）。测得了cisPd（Ph₂PCH₂COO）₂（40）的晶体结构。 2.研究了上述三种钯配合物催化Suzuki偶联反应,优化了反应条件。在室温下,用此反应合成液晶单体化合物,其收率大于90%。催化剂可循环使用三次,催化活性基本保持不变。 3.研究了P⌒O双齿螯合钯配合物Pd（Ph₂PCH₂CH₂O）₂（43）和Pd（Ph₂PCH₂CH（CH₃）O）₂（44）对Suzuki偶联反应的催化作用,结果表明配合物44比43具有更好的催化活性。 4.研究了P⌒N双齿螯合钯配合物[Pd（Ph₂PCH₂CH₂NH₂）₂]Cl₂（45）和[Pd（Ph₂PCH₂CH₂CH₂NH₂）₂]Ch（堑）对Suzuki偶联反应的催化作用,绝大部分偶联产率在95%左右,比P⌒O钯配合物的催化活性更好。 5.探讨了cis-Pd（Ph₂PCH₂COO）₂（40）催化Suzuki偶联反应机理及催化剂分解析出钯黑的原因。更多还原

【Abstract】 Suzuki cross-coupling of aryl bromides with arylboronic acid is one of effective methods to form biphenyl derivatives in organic synthesis. In this thesis, the three series of P, O and P, N bidentate ligands chelated palladium complexes ￡40-46} were designed and synthesized for Suziki cross-coupling reaction. The coupling reaction of aryl bromides with arylboronic acid in the presence of catalytic amount of 40-46 proceeded smoothly under mild reaction conditions （room temperature） with high selectivity and excellent yields, which indicated that the palladium complexes 40-46 are excellent catalysts for Suzuki cross-coupling reactioa Various substrates can be employed in the palladium complexes 40-46 catalyzed coupling reaction, and the new method could be used in industry to prepare biphenyl derivatives. The details are as follows:1. The bidentate P/O ligands were synthesized by improved method under mild reaction conditions in high yields with high purities. The three bidentate P/O palladium complexes, cis-Pd（Ph₂PCH₂COO）₂ （40）, cis-Pd（Ph₂PCH₂CH₂COO）₂ （41） and cis-Pd（o-Ph₂PC₆H₄COO）₂ （42）, were prepared, and the crystal structure of 40_was elucidated.2. The three bidentate palladium complexes mentioned above were used as catalysts in Suzuki cross-coupling. Liquid crystalline compounds were synthesized via one-step process at room temperature in excellent yields （>90%）. These catalysts could be reused for three times without losing their catalytic activities.3. Two bidentate P/O palladium complexes, Pd（Ph₂PCH₂CH₂O）₂ （43） and Pd(Ph₂PCH₂CH（CH₃）O}₂ （44）, were synthesized, and their catalytic activities in Suzuki cross-coupling were investigated. The catalyst 44 shows higher catalytic activity than that of 43.4. Two bidentate P/N palladium complexes, [Pd（Ph₂PCH₂CH₂NH₂）₂]Cl₂ （45） and [Pd（Ph₂PCH₂CH₂CH₂NH₂）₂]Cl₂ （46）, were synthesized, and their catalytic activities in Suzuki cross-coupling were investigated and the high yields of products were obtained in almost case. Both of the catalysts 45 and 46 show higher catalytic activities than that of bidentate P/O palladium complexes.5. The mechanism of the palladium complex 40 catalyzed Suzuki cross-coupling reaction was discussed. The cause of decomposition of catalyst and appearance of palladium black were studied.更多还原