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首页> 外文学位 >I. Abstraction of deuterium from dideuteroglycine by aryl radical: A model for 1,4-aryl diradical reactions with proteins. II. Acyl hydrazines as precursors to acyl radicals: Direct trapping and cyclization studies.
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I. Abstraction of deuterium from dideuteroglycine by aryl radical: A model for 1,4-aryl diradical reactions with proteins. II. Acyl hydrazines as precursors to acyl radicals: Direct trapping and cyclization studies.

机译：I.通过芳基从双去氢甘氨酸提取氘：与蛋白质的1，4-芳基双自由基反应的模型。二。酰基肼作为酰基自由基的前体：直接捕获和环化研究。

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摘要

Part I of this dissertation briefly addresses the mechanism of cytotoxicity of the enediyne antibiotics (e.g., the calicheamicins). Compounds in this class possess the interesting enediyne structural feature, which often following a trigger event that strains the molecule, undergo Bergman cyclization to generate 1,4-aryl diradical intermediates. In the accepted mechanism of action hydrogen from deoxyribose at generally the 5′ or 4 ′ positions, ultimately leading to DNA cleavage. Herein, we contribute evidence that amino acids can be alternative targets for enedlyne-derived aryl radicals. Specifically, aryl radicals were generated in the presence of an α-deuteroglycine model system, and deuterium incorporation was of the amino acid. These results have been published1and add to a growing body of evidence that suggests that enediyne-derived radicals may react with other biomolecules than DNA.; In part II, the use of acyl hydrazines (hydrazides) as precursors to acyl radicals is explored. Many methods exist in the literature for the generation of acyl radicals, but they often require toxic and expensive reagents, limiting their practicality. Alkyl hydrazines (R-NHNH2) have been used as precursors for alkyl radicals to prepare initiators for living free-radical polymerization. This led to the idea of generating acyl radicals from readily available acyl hydrazine precursors (R-CO-NHNH2). Model studies showed that simple acyl hydrazines could be mildly oxidized with loss of N 2 to acyl radicals, which could then be stoichiometrically trapped with nitroxide radicals. Attention was then turned to performing more synthetically useful radical cyclization reactions. Several substrates were prepared and subject to the same mild oxidative conditions to generate acyl radicals which were then subsequently cyclized and trapped with varying degrees of success. A second class of acyl hydrazines was also examined in which substrates substituted with a leaving group (R-CO-NHNH-Lg) were converted to acyl radicals. The subsequent trapping or cyclization of these radicals was also explored.; 1Braslau, R. B.; Anderson, M. O. Tetrahedron Lett. 1998, 39, 4227–4230.
机译：本论文的第一部分简要论述了烯二炔抗生素（例如加利车霉素）的细胞毒性机理。此类化合物具有有趣的烯二炔结构特征，该特征通常在触发事件使该分子拉紧之后，经过Bergman环化反应生成1,4-芳基双自由基中间体。在公认的作用机理中，脱氧核糖中的氢通常在5 '或4 '位置发生，最终导致DNA裂解。在本文中，我们提供证据表明氨基酸可以作为烯二烯衍生的芳基的替代靶标。具体地，在α-氘代甘氨酸模型系统的存在下产生芳基，并且氘掺入氨基酸。这些结果已经发表在 1 上，并增加了越来越多的证据表明，烯二炔基自由基可能与DNA以外的其他生物分子发生反应。在第二部分中，研究了使用酰基肼（酰肼）作为酰基自由基的前体。文献中存在许多产生酰基自由基的方法，但是它们通常需要有毒且昂贵的试剂，从而限制了它们的实用性。烷基肼（R-NHNH 2 ）已被用作烷基自由基的前体，以制备用于自由基聚合的引发剂。这导致了从容易获得的酰基肼前体（R-CO-NHNH 2 ）生成酰基的想法。模型研究表明，简单的酰基肼可被轻度氧化，而N 2 损失为酰基自由基，然后化学计量地被氮氧自由基捕获。然后将注意力转向进行更多可用于合成的自由基环化反应。制备了几种底物，并使其在相同的温和氧化条件下产生酰基，然后将其环化并以不同程度的成功捕获。还检查了第二类酰基肼，其中被离去基团（R-CO-NHNH-Lg）取代的底物被转化为酰基。还研究了这些自由基随后的捕获或环化。 1 布拉斯劳，R。B .; Anderson，M. O. 四面体Lett 。 1998 ， 39 ，4227–4230。

著录项

  • 作者

    Anderson, Marc Oliver.;

  • 作者单位

    University of California, Santa Cruz.;

  • 授予单位 University of California, Santa Cruz.;
  • 学科 Chemistry Organic.
  • 学位 Ph.D.
  • 年度 2001
  • 页码 220 p.
  • 总页数 220
  • 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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