首页> 外文学位 >Part I. A refined synthetic route to a key synthon for (+)-laurencin. Part II. Studies toward development of a general method for stereocontrolled construction of conjugated (E)-enyne subunit required for (+)-laurencin.
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Part I. A refined synthetic route to a key synthon for (+)-laurencin. Part II. Studies toward development of a general method for stereocontrolled construction of conjugated (E)-enyne subunit required for (+)-laurencin.

机译:第一部分。精制合成关键合成子的合成途径,以合成(+)-月桂酸。第二部分对开发用于(+)-劳伦霉素所需的共轭(E)-烯炔亚基的立体控制结构的一般方法的开发的研究。

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摘要

Part I. Improved sequence of reactions to camphor based lactam imide and improved diastereoselectivity of the corresponding Lewis acid promoted [2+2] cycloaddition reaction with phenyl vinyl sulfide are described. Reaction conditions were identified for efficient transformation of maleic anhydride into a fumaric acid derivative for high yielding acylation of camphor based lactam. Modified reaction conditions we utilized to achieve synthetically useful methylaluminum dichloride promoted [2+2] cycloaddition of the lactam imide with phenyl vinyl sulfide with diastereofacial selectivity of greater than 20:1.; Part II. Exploratory studies for construction of a requisite (E)-enyne subunit for (+)-laurencin are described. Allyl barium allylation, sulfoxide chelotropic elimination, anionic sulfone elimination, umplong alkylation, Stille coupling and aldol alkylation were investigated and the factors governing the selectivity of the enyne subunit geometry analyzed. A novel synthon for the stereocontrolled synthesis of ( E)-enyne subunit was identified and synthesized.
机译:第一部分。描述了改进的基于樟脑的内酰胺酰亚胺的反应顺序和相应的路易斯酸促进的与苯基乙烯基硫的[2 + 2]环加成反应的非对映选择性。确定了反应条件,以将马来酸酐有效转化为富马酸衍生物,从而使樟脑基内酰胺高产酰化。我们利用改进的反应条件来实现合成上有用的二氯化甲基铝促进内酰胺与苯基乙烯基硫的[2 + 2]环加成,其非对映体选择性大于20:1。 第二部分。描述了为(+)-laurencin构建必需的( E )-烯炔亚基的探索性研究。研究了烯丙基钡的烯丙基化,亚砜的化学离解,阴离子砜的消除,全烷基烷基化,斯蒂勒偶联和醛醇烷基化,并分析了影响烯炔亚基几何形状选择性的因素。鉴定并合成了一种立体合成( E )-烯炔亚基的新型合成子。

著录项

  • 作者

    Udal, Robert Peter.;

  • 作者单位

    The University of Rochester.;

  • 授予单位 The University of Rochester.;
  • 学科 Chemistry Organic.
  • 学位 Ph.D.
  • 年度 2002
  • 页码 168 p.
  • 总页数 168
  • 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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