Silirane-Mediated Stereoselective Synthesis of Amines

本文介绍了硅杂环丙烷插入反应在氨基醇立体选择性合成中的应用， 提出了本项目是硅烷介导的多氧化合物合成的一个延伸 由Woerpel集团调查。亚胺和亚硝酸盐在Si-C中的区域和立体选择性插入 硅烷键将被开发以形成构象受限的氮杂硅杂环化合物， 相邻的立体碳中心。这些产物将通过亲核反应在结构上进行详细阐述。 加成和环化反应，将通过构象控制立体电子 氮杂硅烷环的偏好。Si-N键的水解或酰化然后将提供Si-N键的水解或酰化。 Si-C键的氧化将释放非对映体富集的1，3-二氨基脲。 氨基醇这个项目是综合吸引力，因为它夫妇简单的起始材料，形成 复杂的产品使用的构象偏好的五元环。氨基醇是 生物活性分子中的共同基序，并且硅烷插入方法的这一进展将 为含氮药物靶标的立体选择性合成提供了新的途径。

The application of silacyclopropane insertion reactivity to the stereoselective synthesis of aminoalcohols is proposed. This project is an extension of the silirane-mediated syntheses of polyoxygenated compounds investigated by the Woerpel group. Regio- and stereoselective insertions of imines and nitrites into theSi-C bonds of siliranes will be developed to form conformationally constrained azasilacyclic compounds with three contiguous stereogenic carbon centers. These products will be elaborated structurally through nucleophilic addition and cyclization reactions that will be controlled stereoelectronically by the conformational preferences of the azasilane ring. Hydroylsis or acylation of the Si-Nbond will then provide the corresponding amine or carbamide, and oxidation of the Si-Cbond will release diastereoenriched 1,3- aminoalcohols. This project is synthetically appealing because it couples simple starting materials to form complicated products using the conformational preferences of a five-membered ring. Aminoalcohols are common motifs in biologically active molecules and this advancement of silirane insertion methodology will provide new approaches for the stereoselective syntheses of nitrogen-containing pharmaceutical targets.