Silacyclopropanes: Building Blocks for Organic Synthesis

描述（由申请人提供）：我们的实验室开创了硅杂环丙烷在有机合成中的应用，并且我们已经证明它们的反应是立体特异性的、立体选择性的和区域选择性的，但是我们仍然缺乏用于它们的合成的温和方法。在上一个资助期间，我们开发了一种在低温下催化亚甲硅烷基单元t-Bu 2Si转移到烯烃的方法。该反应允许合成先前不可能制备的手性官能化硅杂环丙烷和硅杂环丙烯。 该提议描述了金属催化的亚甲硅烷基转移到宽范围的反应性官能团。初步的实验表明，新的范例的反应硅烯中间体和应用这些反应的立体选择性合成是可能的。在资助期内，我们将致力于以下硅烯转移化学领域的重要课题：（1）制备高度官能化的三元环硅化合物，探索其反应作为立体选择性合成的新方法。(2)我们将研究亚甲硅烷基转移到新的官能团，我们将使用这些反应作为方法来获得合成有用的官能团。(3)我们将研究硅上新的、更容易官能化的基团的发展，并且我们将探索硅烯转移的新方法。 这项建议将对公众健康产生重大影响。在单一操作中将简单有机化合物转化为复杂产品的能力是制造新化学品的强大方法。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制造药剂。

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.