SILACYCLOPROPANES--BUILDING BLOCKS FOR ORGANIC SYNTHESIS

描述：首席调查员指出，尽管 已探索了硅环丙烷的基本化学，这些 化合物尚未用于有机合成。他报告说 初步数据表明，这些应变环硅烷是有用的。 用于构建多氧有机化合物的积木。 据称，硅环丙烷作为掩蔽的1，3-二醇，并新 碳-碳键具有高的立体选择性(大于 98%)。首席调查员表示，该提案 丙酸(和二丙酸酯)的详细构造方法 由乙醛单元终止的单元，该体系结构 功能，如果它具有防病毒功能，则很难安装 立体化学，是许多治疗上重要的化合物所共有的， 如两性霉素B和制霉菌素A1，是多烯的代表 大环内酯类抗生素。值得注意的是，这些化合物是最 对抗系统性真菌感染的有效药物，发生在 接受癌症化疗和免疫功能低下的患者 移植，以及艾滋病患者和新方法 多烯大环内酯类化合物及其类似物的制备 因为进行结构-活性研究对这一进展很重要 健康科学领域的专家。 首席调查员特别指出，以下将是 证明：(1)甲酰胺插入硅环丙烷 将导致合成多氧化合物的新方法， 最终导致甜叶菊糖醇的全合成，这是一种性信息素 破坏储粮的有害生物；(2)金属催化 硅烯转移反应等反应将提供新的合成方法 以及金属催化的插入反应将 生成有用的多元醇亚结构；(3)含芳香族的硅环丙烷 将研究硅原子上的取代基，以确定它们的 反应性；以及(4)硅烷改性氧化为 酒精将会被确定。

DESCRIPTION: The principal investigator notes that although the fundamental chemistry of silacyclopropanes has been explored, these compounds have not been utilized in organic synthesis. He reports that preliminary data suggest that these strained-ring silanes are useful building blocks for the construction of polyoxygenated organic compounds. It is stated that the silacyclopropane acts as a masked 1,3-diol, and new carbon-carbon bonds are formed with high stereoselectivity (greater than 98 percent). The principal investigator indicates that the proposal details methods for the construction of propionate (and dipropionate) units terminated by an acetyaldehyde unit and that this architectural feature, which can be difficult to install if it possesses anti stereochemistry, is shared by many therapeutically important compounds, such as amphotericin B and nystatin A1, representatives of the polyene macrolide antibiotics. It is noted that these compounds are the most effective drugs for combating systemic fungal infections, which occur in immuno-compromised patients undergoing cancer chemotherapy and transplants, as well as AIDS patients and that new methods which facilitate the preparation of the polyene macrolides and their analogs for conducting structure-activity studies are important to the progress of the health sciences. The principal investigator states that in particular, the following will be demonstrated: (1) the insertion of formamides into silacyclopropanes will lead to new methods for the synthesis of polyoxygenated compounds, culminating in the total synthesis of stegobiol, the sex pheromone of a pest responsible for the destruction of stored grain; (2) metal-catalyzed reactions such as silylene transfer reactions will provide new syntheses of silacyclopropanes, and metal-catalyzed insertion reactions will generate useful polyol substructures; (3) silacyclopropanes with aromatic substituents on the silicon atom will be investigated to determine their reactivity; and (4) the generality of a modified oxidation of silanes to alcohols will be determined.