Nature and Application of Chiral Sulfinylallyl and Allylphosphonyl Anions (Chemistry)

有机和大分子化学计划支持该项目，该项目涉及新型含硫和含磷试剂的开发，用于制备各种具有生物重要性的天然化合物。这些试剂被设计用于进行各种重要的有机反应，其中许多具有异常高的立体专一性。碳-碳键的对映选择性形成在手性有机分子的合成中是极其重要的。最近，该研究小组开发了一种通用的、简单的环化工艺，可以制备出具有高到优异光学纯度的环状化合物，即在环烯酮上加入手性亚砜烯丙基阴离子1,4，可获得70-97%的ee，手性烯丙基膦基阴离子可获得88-98%的ee。研究手性亚砜基和膦烯丙基阴离子的立体定向1,4加成反应的一般范围、机理和通用性，将有助于更好地了解阴离子的结构，并进一步了解它们在有机合成中的应用。利用这些方法可以实现抗肿瘤药物、毛霉烯、吲哚吡啶类生物碱和许多其他二萜类化合物的对映选择性全合成。

The Organic and Macromolecular Chemistry Program is supporting this project which deals with the development of novel sulfur- and phosphorus-containing reagents to be used to prepare a variety of naturally occurring compounds of biological importance. These reagents are designed to carry out a wide variety of important organic reactions, many of them with an unusually high degree of stereospecificity. The enantioselective formation of carbon-carbon bond is extremely important in the synthesis of chiral organic molecules. Recently, this research group has developed a general and facile process for annulation which allows the preparation of these ring compounds in high to excellent optical purities, i.e. 1,4 gamma-addition of chiral sulfinylallyl anions to cyclic enones provided 70-97% ee, and chiral allylphosphonyl anions provided 88-98% ee. Studies of the general scope, mechanism and versatility of these stereospecific 1,4-addition reactions of chiral sulfinyl- and phosphonylallyl anions will provide better understanding of the structures of the anions and further information on their utility in organic synthesis. Enantioselective total syntheses of antitumor agents, trichothecenes, indolizidine alkaloids, and many other diterpenoids will be realized by utilizing these methods.