Silacyclopropanes: Building Blocks for Organic Synthesis

描述（申请人提供）：我们的实验室开创了硅杂环丙烷在有机合成中的应用，并证明了它们的反应具有立体特异性、立体选择性和区域选择性，但我们仍然缺乏温和的合成方法。在上一个资助期间，我们开发了一种在低温下催化硅烯单元 t-Bu2Si 转移到烯烃的方法。该反应可以合成以前不可能制备的手性官能化硅杂环丙烷和硅杂环丙烯。 该提案描述了金属催化的亚硅基转移到广泛的反应性官能团。初步实验表明，亚硅中间体反应的新范例以及这些反应在立体选择性合成中的应用是可能的。在资助期间，我们将解决硅基转移化学中的以下重要问题：（1）我们将制备高功能化的三元环硅化合物，并探索它们的反应作为立体选择性合成的新方法。 (2)我们将研究亚硅基转移到新的官能团，并且我们将使用这些反应作为获得合成上有用的官能团的方法。 (3)我们将研究开发新的、更容易官能化的硅基团，并探索硅烯转移的新方法。 该提案将对公共卫生产生重大影响。在一次操作中将简单的有机化合物转化为复杂的产品的能力是制造新化学品的有力方法。这些新方法可能对制药行业的化学家有用，他们需要新的方法来更有效地生产药剂。

DESCRIPTION (provided by applicant): Our laboratory has pioneered the applications of silacyclopropanes in organic synthesis, and we have demonstrated that their reactions are stereospecific, stereoselective, and regioselective, but we still lacked a mild method for their synthesis. During the last funding period we developed a method for catalyzing the transfer of the silylene unit t-Bu2Si to alkenes at low temperatures. This reaction allows for the synthesis of chiral, functionalized silacyclopropanes and silacyclopropenes that had been impossible to prepare previously. This proposal describes metal-catalyzed silylene transfer to a broad range of reactive functional groups. Preliminary experiments suggest that new paradigms for the reactions of silylene intermediates and applications of these reactions to stereoselective synthesis are possible. During the funding period, we will address the following important issues in silylene transfer chemistry: (1) We will prepare highly functionalized three-membered ring silicon compounds, and we will explore their reactions as new methods for stereoselective synthesis. (2) We will examine silylene transfer to new functional groups, and we will use these reactions as methods to access synthetically useful functional groups. (3) We will examine the development of new, more easily functionalized group on silicon, and we will explore new methods for silylene transfer. This proposal will have considerable implications for public health. The ability to convert simple organic compounds to complex products in a single operation is a powerful approach to making new chemicals. These new methodologies may be useful to chemists in the pharmaceutical industry, who require new ways to make pharmaceutical agents more efficiently.