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The Stetter reaction: Scope and mechanistic investigation.

机译：斯特特尔的反应：范围和机制研究。

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摘要

Since the isolation and characterization of stable imidazolinylidene carbenes by Arduengo in 1991, chemists have been increasingly fascinated by their potential as modifying ligands on transition metals. However, it was not until Ukai demonstrated the efficacy in the benzoin reaction that the use of stable nucleophilic carbenes as catalysts was used for organic transformations. The last 10 years in particular have seen a tremendous explosion of interest in this area, with new reactivity manifolds having been developed across a range of reaction subtypes.;The highly enantioselective intramolecular Stetter reaction has been expanded to include the formation of tetrasubstituted stereocenters. The reaction is mild, general, and tolerates aromatic, aliphatic, sulfur, oxygen, and nitrogen tethering of aldehyde and Michael acceptor. The current substrate scope includes compounds with varying electronics and sterics.;A mechanistic investigation into the intramolecular Stetter reaction has been conducted. The rate law of the reaction was determined and coupled with kinetic isotope effects, competition experiments and calculations to suggest that proton transfer is rate determining. These results provide the foundation for future development of better catalysts and expansion of substrate scope. The inherent tunability of nucleophilic carbenes as catalysts promises great latitude in overcoming issues associated with functional group compatibility, turnover frequency, turnover number and, naturally, expansion of substrate type. This suggests that nucleophilic carbene catalysts will likely remain useful tools in organic synthesis for the foreseeable future.
机译：自1991年Arduengo分离并鉴定了稳定的咪唑啉亚基卡宾烯以来，化学家对其在过渡金属上修饰配体的潜力越来越着迷。然而，直到Ukai证明在安息香反应中的功效后，才使用稳定的亲核碳烯作为催化剂进行有机转化。特别是在最近的十年中，该领域引起了极大的兴趣爆炸，已经在一系列反应亚型中开发了新的反应性歧管。高对映选择性分子内Stetter反应已经扩展到包括四取代的立体中心的形成。该反应是温和的，一般的，并且可以耐受醛和迈克尔受体的芳族，脂族，硫，氧和氮的束缚。目前的底物范围包括具有不同电子和空间位点的化合物。;已对分子内Stetter反应进行了机理研究。确定了反应的速率规律，并结合了动力学同位素效应，竞争实验和计算结果，表明质子转移是速率的决定因素。这些结果为将来开发更好的催化剂和扩大底物范围提供了基础。亲核碳烯作为催化剂的固有可调性有望在解决与官能团相容性，周转频率，周转数以及自然地扩展底物类型相关的问题上具有很大的自由度。这表明在可预见的将来，亲核卡宾催化剂可能仍将是有机合成中的有用工具。

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  • 作者

    Moore, Jennifer Lynn.;

  • 作者单位

    Colorado State University.;

  • 授予单位 Colorado State University.;
  • 学科 Chemistry Organic.
  • 学位 Ph.D.
  • 年度 2009
  • 页码 113 p.
  • 总页数 113
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 有机化学;
  • 关键词

  • 入库时间 2022-08-17 11:38:26

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