New Intermolecular Traps of Captodative Stabilized and OtherRadicals: Studies Toward Radical Based Asymmetric Synthesis of Amino Acids

本项目将涉及捕获稳定自由基的分子间自由基捕获研究。这项工作在两个主要领域具有重要意义：1)开发新的分子间自由基陷阱；2)使用手性甘氨酸自由基模板进行天然和非天然氨基酸的不对称合成。鉴于自由基在有机合成中的巨大作用，迫切需要开发新的分子间自由基陷阱。将开发的自由基陷阱包括硝基酮、亚硝基锡酸盐、乙烯基氮嘧啶（用于合成烯丙胺和吡啶）、烯醇锡烷、锡炔和手性脱氢丙氨酸。对于氨基酸的不对称合成，将研究几种手性甘氨酸自由基模板，包括手性二酮哌嗪、恶唑烷和9-苯基薄荷醇氨基酸酯。手性甘氨酸自由基的分子间捕获反应将与已建立的自由基诱捕剂（如烯丙基和乙烯基锡烷）和新型自由基诱捕剂一起进行。这项工作将对自由基化学和不对称氨基酸合成领域做出重要贡献。研究计划补助金使以前没有获得独立的联邦研究支持的妇女能够制定具有竞争力的研究计划。该项目涉及捕获稳定的自由基，即具有不成对电子的分子，用于构建有机分子。这类反应在有机化学中具有广泛的适用性，并可作为其他有机合成方法的补充。

This project will involve the study of intermolecular radical trapping of captodative stabilized radicals. This work has important implications in two major areas: 1) the development of new intermolecular radical traps and 2) the use of chiral glycine radical templates for the asymmetric synthesis of natural and non-natural amino acids. Given the tremendous utility of radicals in organic synthesis there is a real need for the development of new intermolecular radical traps. Radical traps that will be developed include nitrones, stannyl nitronates, vinyl aziridines (for both the synthesis of allyl amines and pyrrolidines), enol stannanes, stannyl alkynes, and chiral dehydroalanines. For the asymmetric synthesis of amino acids, several chiral glycine radical templates will be investigated including a chiral diketo piperazine, oxazolidine, and 9-phenyl menthol amino acid ester. Intermolecular trapping reactions of the chiral glycine radicals will be carried out with both established radical traps (such as allyl and vinyl stannanes) and with the novel radical trapping agents. This work will be an important contribution to the areas of radical chemistry and asymmetric amino acid synthesis. %%% Research Planning Grants enable women who have not had prior independent Federal research support to develop a competitive research proposal. This project involves the trapping of stabilized free radicals, i.e., molecules with unpaired electrons, for the construction of organic molecules. Such reactions may have wide applicability in organic chemistry and complement other organic synthesis methods.