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Photodecarbonylation of crystalline beta,gamma-unsaturated ketones and its application to preparative scale synthesis of adjacent quaternary centers.

机译：晶体β，γ-不饱和酮的光脱羰作用及其在相邻四元中心的制备规模合成中的应用。

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摘要

Reactions in crystals often proceed with selectivity and efficiency that rival enzymatic processes. Our group is developing the photochemical decarbonylation of crystalline ketones as a general strategy for the stereospecific construction of adjacent chiral quaternary centers. This thesis will discuss the advances and general applicability that have been made to advance this methodology and make it a more robust synthetic method.; Chapter 1, will provide a comprehensive review of photochemical decarbonylation in crystals. The factors that will be discussed include reactions in crystals, phase transitions, and ketone alpha-substituents. This will give the reader an understanding of the scope of this novel synthetic method, including its advantages and limitations. Chapter 1 will set the stage for the developments that will be presented in the remainder of the thesis. The history of photochemical decarbonylation from its earliest beginnings in the 1960's through 2005 will be elaborated.; The photochemistry and synthesis of 2-(cycloalken-1-yl)cycloalkanones will be discussed in Chapter 2. Factors that influence the reactivity of beta,gamma-unsaturated ketones will be discussed, including competing reactions. Chapter 3, will deal mainly with the synthesis of beta,gamma-unsaturated ketones. The beginnings of synthetic routes to optically active compounds are described. A novel variation of Michael reactions between imines and alkynes, to give bis-beta,gamma-unsaturated ketones, was used to synthesize decarbonylation precursors. The development of enantioselective versions of these reactions which could then undergo decarbonylation to give the optically active cyclopentane products is an important focus of this chapter. Crystal engineering and the preparative scale potential of decarbonylation in crystals of the compounds synthesized in Chapter 3 will be described in Chapter 4.; Chapter 5 discusses the synthesis and photochemistry of alpha-cyclopropyl ketones and cyclopropenones. These systems exhibit interesting behavior due to ring strain. alpha-Cyclopropyl ketones can potentially be used as radical clocks to understand the time scales involved in the decarbonylation reaction.
机译：晶体中的反应通常以与酶促过程相媲美的选择性和效率进行。我们小组正在开发晶体酮的光化学脱羰基反应，作为相邻手性四元中心立体构象的一般策略。本文将讨论改进该方法并使其成为更可靠的合成方法所取得的进展和普遍适用性。第1章将全面回顾晶体中的光化学脱羰作用。将讨论的因素包括晶体中的反应，相变和酮α-取代基。这将使读者了解这种新颖的合成方法的范围，包括其优点和局限性。第一章将为本文的其余部分介绍的发展奠定基础。光化学脱羰的最早历史将在1960年代到2005年进行阐述。第2章将讨论2-（环烯基-1-基）环烷酮的光化学和合成。将讨论影响β，γ-不饱和酮反应性的因素，包括竞争性反应。第三章将主要讨论β，γ-不饱和酮的合成。描述了合成光学活性化合物的途径的开始。亚胺和炔烃之间的迈克尔反应的一种新颖的变化，以得到双-β，γ-不饱和酮，被用来合成脱羰前体。这些反应的对映选择性形式的发展，然后可以进行脱羰反应以生成光学活性的环戊烷产物，是本章的重点。第3章中将描述晶体工程和第3章中合成的化合物晶体中脱羰基的制备规模电位。第5章讨论了α-环丙基酮和环丙烯酮的合成和光化学。这些系统由于环应变而表现出有趣的行为。 α-环丙基酮可潜在地用作自由基钟，以了解脱羰反应中涉及的时间尺度。

著录项

  • 作者

    Mortko, Christopher Joseph.;

  • 作者单位

    University of California, Los Angeles.;

  • 授予单位 University of California, Los Angeles.;
  • 学科 Chemistry Organic.
  • 学位 Ph.D.
  • 年度 2005
  • 页码 283 p.
  • 总页数 283
  • 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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