Silacyclopropanes: Building Blocks for Organic Synthesis

描述(申请人提供)：本实验室已率先在有机合成中应用了硅环丙烷，并证明了它们的反应具有立体专一性、立体选择性和区域选择性，但我们仍然缺乏一种温和的合成方法。在上一次资助期间，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。该反应允许合成手性、官能化的硅环丙烷和硅环丙烯，这是以前不可能制备的。 这一建议描述了金属催化的硅烯转移到广泛的反应性官能团。初步实验表明，硅烯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，我们将解决硅烯转移化学中的以下重要问题：(1)我们将制备高官能化的三元环硅化合物，并探索其反应作为立体选择性合成的新方法。(2)我们将考察硅烯向新官能团的转移，并将这些反应作为获得合成有用官能团的方法。(3)我们将研究硅上新的、更容易官能化的基团的发展，并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。在一次操作中将简单的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。这些新的方法可能对制药业的化学家有用，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.