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

有机和高分子化学计划是支持 该项目涉及开发新型硫- 和含磷试剂以用于制备 各种天然存在的生物化合物 重要性 这些试剂旨在进行广泛的 各种重要的有机反应，其中许多与 异常高的立体特异性。 碳-碳键的对映选择性形成是 在手性有机化合物的合成中极为重要 分子。 最近，这个研究小组开发了一个 一般和容易的环化过程， 这些环化合物的制备具有高至优异的 光学纯度，即手性的1，4 γ-加成 亚磺酰基烯丙基阴离子与环烯酮的反应提供70- 97%ee，和 手性烯丙基膦酰基阴离子提供88- 98%ee。 这些技术的一般范围、机制和通用性 手性亚磺酰基-和 膦酰基烯丙基阴离子将提供更好的理解 阴离子的结构和进一步的信息， 在有机合成中的应用 不对称全合成 抗肿瘤剂，二萜类，吲哚里西啶生物碱， 和许多其它二萜类化合物将通过利用这些化合物来实现， 方法.

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.