CAREER: Chemical Methods for Organic Synthesis Using Nucleophilic Allyl- and Alkylmetal Catalysts

职业：使用亲核烯丙基和烷基金属催化剂进行有机合成的化学方法

• 批准号: 0847273
• 负责人: Elizabeth Jarvo
• 金额: $ 55万
• 依托单位: University of California-Irvine
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2009
• 资助国家: 美国
• 起止时间: 2009-03-01 至 2014-02-28
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0847273&HistoricalAwards=false
• 关键词: CAREER; Chemical; Methods; Organic; Synthesis

Proposal Abstract This project will address the development of catalyst-controlled asymmetric allylation and alkylation reactions. While many methods for enantioselective allylation and alkylation reactions exist, new methods are required for efficient and practical reactions of complex synthetic intermediates. A central hypothesis is that nucleophilic allylmetal and alkylmetal complexes will be formed in situ by transmetallation mechanisms and these species will undergo ligand-controlled reactions with electrophiles. Preliminary studies have uncovered a new class of nucleophilic allylpalladium complexes with bidentate neutral N-heterocyclic carbene ligands, which have been used to develop catalytic allylation reactions of N-acylpyrroles and alkylidene malononitriles. The development of stereoselective conjugate allylation reactions of broad scope with mild reaction conditions is planned. In addition, new mechanisms for alkylation reactions of electrophiles by generating alkylmetal complexes from boronic acids with first row transition metals will be proposed. Studies to elucidate the mechanisms of the transformation will also be performed. With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Professor Elizabeth Jarvo of the Department of Chemistry at the University of California, Irvine. Professor Jarvo's research efforts revolve around the development of selective methods for the formation of C-C bonds. Such chemistry will contribute to environmentally benign methods for chemical synthesis as the transformations will be practical and efficient, which will minimize the environmental cost of the transformation. Successful development of the methodology will have an impact on synthesis in the pharmaceutical and agricultural industries.

摘要本计画将致力于发展催化剂控制的不对称烯丙基化与烷基化反应。虽然存在许多用于对映选择性烯丙基化和烷基化反应的方法，但需要新的方法用于复杂合成中间体的有效和实用的反应。 一个中心的假设是，亲核的烯丙基金属和烷基金属配合物将形成原位transmetabolites机制，这些物种将进行配体控制的亲电反应。初步研究发现了一类新的亲核烯丙基钯与双齿中性N-杂环卡宾配体的配合物，其已被用于发展N-酰基吡咯和烷叉丙二腈的催化烯丙基化反应。 发展了反应条件温和、反应范围广的立体选择性共轭烯丙基化反应。 此外，还提出了由硼酸与第一行过渡金属生成烷基金属络合物的亲电试剂烷基化反应的新机理。 还将进行研究以阐明转化的机制。 有了这个奖项，有机和高分子化学计划是支持教授伊丽莎白贾沃的化学系在加州大学欧文分校的研究。 Jarvo教授的研究工作围绕着C-C键形成的选择性方法的发展。 这种化学将有助于环境友好的化学合成方法，因为转化将是实用和有效的，这将最大限度地减少转化的环境成本。该方法的成功开发将对制药和农业工业的合成产生影响。