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首页> 外文学位 >I. Copper Chemistry in Water at Room Temperature II. Aryl Carbon-Hydrogen Functionalization at Room Temperature III. Atroposelective Syntheses of Axially Chiral Biaryls.
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I. Copper Chemistry in Water at Room Temperature II. Aryl Carbon-Hydrogen Functionalization at Room Temperature III. Atroposelective Syntheses of Axially Chiral Biaryls.

机译：I.室温下水中的铜化学II。室温下芳基碳氢官能化III。轴向手性联芳基的对映选择性合成。

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The first part of this dissertation describes copper hydride chemistry under environmentally attractive conditions by taking advantage of micellar catalysis. Reactions can be performed in water at room temperature. The combination of silane PMHS, nonracemic ligand, and amphiphile has led to a viable, "greener" method for this otherwise well-established transformation normally run in organic solvents at low temperature. In addition, the Cu-catalyzed conjugate addtion of carbon nucleophiles can be done in pure water, even though it as yet has not synthetically useful.;The second part focuses on facile C--H activation reactions of aryl ureas with arylboronic acids and arcrylates at room temperature catalyzed by a dicationic palladium complex. Some evidences as the mechanisms involved were also obtained. A cationic Pd(II) complex was found to smoothly react with aryl ureas to rapidly produce the corresponding cationic palladacycle at room temperature. The structure of the palladacycle was determined by X-ray analysis.;Finally, significant progress has been made towards the atropselective syntheses of axial chiral biaryl natural products in our group. During the course of these studies, an asymmetric total synthesis of (+)-korupensamine B has been completed in 7% overall yield, with a longest sequence of 18 steps from commercially available materials. This concise synthesis features a stereocontrolled biaryl coupling between the highly functionalized naphthyl and THIQ subsections. The construction of the naphthylisoquinoline framework may invoke pi-stacking interactions as a source of stereocontrol. Furthermore, in order to make the tether ligand reusable, an ester linker instead of ether linker was redesigned and synthesized for the synthesis of the AB ring system of vancomycin. Thirdly, combining these concepts with previous studies, we are aiming at enantioselective synthesis of (-)-marinopyrrole A, via a direct coupling of two fully elaborated pyrrole units. The synthetic pathway to fully elaborated pyrrole units has been developed. Further studies on vancomycin and marinopyrrole A are currently being investigated in our laboratories.
机译：本文的第一部分描述了利用胶束催化在环境有吸引力的条件下氢化铜的化学反应。反应可以在室温下在水中进行。硅烷PMHS，非外消旋配体和两亲物的组合已为通常在低温下在有机溶剂中进行的这种确定的转化方法提供了可行的“绿色”方法。此外，即使在碳纳米管中，铜催化的亲核碳原子的共轭加成反应也可以在纯净水中完成，尽管目前尚无合成价值。第二部分着眼于芳基脲与芳基硼酸和弓形酸酯的简便的CH-H活化反应。在室温下由钯离子络合物催化。还获得了一些证据，作为所涉及的机制。发现阳离子Pd（II）配合物可与芳基脲平稳反应，从而在室温下快速产生相应的阳离子四氢环磷酰胺。通过X射线分析确定了Palladacycle的结构。最后，在我们组中，轴向手性联芳基天然产物的Atropselective合成取得了重大进展。在这些研究过程中，已经完成了（+）-甲氨苯胺B的不对称全合成，总收率为7％，其中最长的18步序列来自于可商购的材料。这种简洁的合成方法在高度官能化的萘基和THIQ小片段之间建立了立体控制的联芳基偶联。萘基异喹啉框架的构建可以调用pi堆积相互作用作为立体控制的来源。此外，为了使系链配体可重复使用，重新设计了酯连接基而不是醚连接基，以合成万古霉素的AB环系统。第三，将这些概念与以前的研究相结合，我们的目标是通过两个完全加工的吡咯单元的直接偶联，对映体合成（-）-萘并吡咯A。已开发出完全合成吡咯单元的合成途径。目前在我们的实验室中对万古霉素和马诺吡咯A进行了进一步的研究。

著录项

  • 作者

    Huang, Shenlin.;

  • 作者单位

    University of California, Santa Barbara.;

  • 授予单位 University of California, Santa Barbara.;
  • 学科 Chemistry Inorganic.;Chemistry Organic.
  • 学位 Ph.D.
  • 年度 2011
  • 页码 293 p.
  • 总页数 293
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

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