Nitrile Anions: Uunmasking Fundamental Reactivity

该项目将继续开发新的金属氰化物的立体选择性烷基化反应。将特别关注对环境无害的烷基化反应，以寻求产生丁腈阴离子的新方法。将对烯烃烷基化进行详细的机理分析，作为开发密集取代双环酮的一般合成的前奏。从这些反应中得到的基本见解将被用来开发一种手性烷基化策略，用于组装连续的三四元立体中心。通过这一奖项，有机和高分子化学项目支持了杜肯大学化学系弗雷泽·F·弗莱明教授的研究。弗莱明教授的研究重点是金属化的腈的新反应，这些反应不能通过相应的羰基衍生物的烷基化来实现。该化学将有助于环境友好的化学合成方法，解决长期存在的合成受阻手性中心的困难，并提供对金属化氰化物性质的基本见解。实现这些目标将影响制药和农业特别感兴趣的小有机分子的合成。

This project will continue the development of new stereoselective alkylations of metalated nitriles. New methods of generating nitrile anions will be pursued with particular attention on environmentally benign alkylations. Detailed mechanistic analysis of alkene alkylations will be undertaken as a prelude to developing a general synthesis of densely substituted bicyclic ketones. Fundamental insight from these reactions will be used to develop a chiral alkylation strategy for assembling contiguous tertiary-quaternary stereocenters. With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Professor Fraser F. Fleming of the Department of Chemistry at Duquesne University. Professor Fleming's research focuses on new reactions of metalated nitriles that are unable to be achieved through alkylation of the corresponding carbonyl derivatives. The chemistry will contribute to environmentally benign methods for chemical synthesis, address the long-standing difficulty of synthesizing hindered chiral centers, and provide fundamental insight into the nature of metalated nitriles. Achieving these goals will impact the synthesis of small organic molecules of particular interest to pharmaceutical and agricultural industries.