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首页> 外文学位 >Transition metal-catalyzed cross-coupling methodologies for carbon-carbon bond and carbon-nitrogen bond formation.
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Transition metal-catalyzed cross-coupling methodologies for carbon-carbon bond and carbon-nitrogen bond formation.

机译：过渡金属催化的交叉偶联方法用于碳-碳键和碳-氮键的形成。

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摘要

The copper(I) carboxylate-mediated, palladium-catalyzed coupling of various thioorganics has been proved efficient with both boronic acids and organo-tri-n-butylstannanes. However, certain limitations are to be studied. As a case in point, the coupling of thiol esters have been successfully developed for various substituents on the thiol ester (aromatic, heteroaromatic, aliphatic), and with aromatic, heteroaromatic, and alkenylboronic acids, but not with aliphatic boronic acids. An exploration of extending the thiol ester cross-coupling protocol to include aliphatic organoboron reagents was therefore performed. Through the use of B-alkyl-9-BBN derivatives, cross-coupling of thiol esters was broadened to include aliphatic boron reagents. In the presence of a base, aryl-alkyl and alkyl-alkyl ketones with a variety of functional groups were synthesized in moderate to excellent yields. Moreover, an investigation of the cross-coupling of alkenyl sulfides with organoboron reagents was also carried out to fulfill the protocol. It was found that olefins with trans configuration could be obtained in good yields using a rhodium(I) catalyst in the presence of a copper(I) carboxylate mediator.; Application of the copper(I) carboxylate-mediated, palladium-catalyzed cross-couplings of thioorganics to solid phase synthesis was also explored. Thiol esters and heteroaromatic thioethers were attached to different solid supports via different linkers. By using water-soluble Pd catalysts, the coupling of modified polymers with boronic acids successfully gave the desired coupling products in the solution phase.; Transition metal-catalyzed reactions of various heteroatom-heteroatom reactants with mild reaction partners would provide new and mild approaches for carbon-heteroatom bond formation. Carbon-nitrogen bond formation from a series of N = O and N-O compounds has been investigated. A copper(I)-mediated reductive amination of boronic acids with nitroso aromatics was observed, giving unsymmetrical diarylamines in good yields. The reaction was accomplished by using a stoichiometric quantity of copper(I) or catalytic copper(I) carboxylate and an external reducing agent. Hydroxylamine derivatives, with lower oxidation state than nitroso compounds, were then employed in the copper-mediated amination of boronic acids. Amides were obtained from O-substituted hydroxamic acids in formation of carbon-nitrogen bond. O-Substituted oximes also participated in the copper(I)-catalyzed amination of boronic acids or organotin compounds, giving ketimines in good yields.
机译：硼酸和有机三正丁基锡烷均被证明是羧酸铜（I）介导的，钯催化的各种硫代有机化合物的偶联。但是，要研究某些限制。作为一个例子，已经成功地开发了硫醇酯的偶联用于硫醇酯上的各种取代基（芳族，杂芳族，脂族），并与芳族，杂芳族和烯基硼酸，但是与脂族硼酸没有。因此，进行了将硫醇酯交叉偶联方案扩展至包括脂族有机硼试剂的探索。通过使用B-烷基-9-BBN衍生物，硫羟酸酯的交叉偶联扩大到包括脂族硼试剂。在碱的存在下，以中等至优异的产率合成了具有各种官能团的芳基-烷基和烷基-烷基酮。此外，还对烯基硫与有机硼试剂的交叉偶联进行了研究，以实现该方案。已经发现，在羧酸铜（I）介体存在下，使用铑（I）催化剂可以高收率获得具有反式构型的烯烃。还探讨了羧酸铜（I）介导的，钯催化的硫代有机物交叉偶联在固相合成中的应用。硫醇酯和杂芳族硫醚通过不同的接头连接到不同的固体支持物上。通过使用水溶性Pd催化剂，改性聚合物与硼酸的偶联成功地在溶液相中产生了所需的偶联产物。各种杂原子-杂原子反应物与轻度反应伙伴的过渡金属催化反应将为碳-杂原子键的形成提供新的，温和的方法。已经研究了由一系列N = O和N-O化合物形成的碳氮键。观察到亚硝基芳族化合物经铜（I）介导的硼酸还原胺化反应，得到不对称的二芳基胺，收率很高。该反应通过使用化学计量的铜（I）或催化的羧酸铜（I）羧酸盐和外部还原剂来完成。然后将氧化态比亚硝基化合物低的羟胺衍生物用于铜介导的硼酸胺化。酰胺是从O-取代的异羟肟酸中形成碳-氮键而获得的。 O取代的肟还参与了铜（I）催化的硼酸或有机锡化合物的胺化反应，从而获得了高产率的酮亚胺。

著录项

  • 作者

    Yu, Ying.;

  • 作者单位

    Emory University.;

  • 授予单位 Emory University.;
  • 学科 Chemistry Organic.
  • 学位 Ph.D.
  • 年度 2004
  • 页码 237 p.
  • 总页数 237
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 有机化学;
  • 关键词

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