SYNTHETIC ORGANOSILICON CHEMISTRY

我们打算在两个重要的合成领域进行基础研究， 有机硅化学：硅杂配合物用于阴离子络合 以及从硅到碳的手性转移。 这两个领域都有 对合成有机物和医药 化学. 我们建议研究几种聚硅烷的络合能力 卤素原子的反应 特别是，我们计划制备分子， 位于分子三角形顶点的三个或四个硅原子 和四面体，我们称之为硅冠化合物， 硅树脂 我们计划研究这些 硅丙交酯结合带负电荷的原子如卤化物和一些 多原子阴离子（碳酸根、硝酸根、磷酸根）。 如果这些 硅橡胶的结合力和我们预期的一样强，它们应该会打开一个 一个全新的研究领域，即非溶剂化的生成和反应 （非极性有机化合物中的“游离”或“裸露”金属离子、阳离子甚至质子） 溶剂. 这些非溶剂化亲电体对重要的 有机反应，例如，Diels-Alder反应，羟醛缩合， 傅-克反应等，将得到充分的测试，有可能 改善或改变这些反应的过程。 在第二个方面，我们提出了制备手性三烷基硅基衍生物的方法 （甲硅烷基烯醇醚、甲硅烷基腈、甲硅烷基丁腈等）和调查 它们与前手性分子的反应 我们希望看到大量的 从硅到碳的手性转移，这是一个还不太好的过程， 在有机硅化学中得到证实。 这样一来， 轻松制备大量重要有机分子（例如， 糖、大环内酯、氨基酸等）在其正确光学纯 通过利用硅处的手性作为唯一的 不对称 这一进程如果成功，将对 合成有机化学和药物化学。

We intend to carry out basic research in two important areas of synthetic organosilicon chemistry: the use of silacavitands for anion complexation and chirality transfer from silicon to carbon. Both of these areas have the potential for a major contribution to synthetic organic and medicinal chemistry. We propose to investigate the complexing ability of several polysilanes toward halogen atoms. In particular we plan to prepare molecules with three or four silicon atoms located at the vertices of molecular triangles and tetrahedra, respectively, compounds we call silacrowns and silacryptands. We plan to study the strength with which these silacryptands bind negatively charged atoms such as the halides and some polyatomic anions (carbonate, nitrate, phosphate). Should these silacryptands bind as strongly as we anticipate, they should open up an entire new field of study, namely the generation and reaction of unsolvated ("free" or "naked" metal ions, cations, and even protons in apolar organic solvents. The effect of these unsolvated electrophiles on important organic reactions, e.g., Diels-Alder reaction, aldol condensation, Friedel-Crafts reaction, etc., will be fully tested, with the potential for improving or altering the course of these reactions. In the second area, we propose to prepare chiral trialkylsilyl derivatives (silyl enol ethers, silyl nitriles, silyl hydrides, etc.) and investigate their reactions with prochiral molecules. We expect to see substantial chirality transfer from silicon to carbon, a process as yet not well demonstrated in organosilicon chemistry. In this way one would be able to prepare easily very large numbers of important organic molecules (e.g., sugars, macrolides, amino acids, etc.) in their correct optically pure forms by utilizing the chirality at silicon as the only source of asymmetry. This process, if successful, would be of great value to synthetic organic and medicinal chemistry.