Palladium-Catalyzed Stereoselective Allylic Alkylation of Carboxylic Acids, Esters, and Nitriles

钯催化的羧酸、酯和腈的立体选择性烯丙基烷基化

• 批准号: 35039324
• 负责人: Professor Dr. Manfred Braun
• 金额: --
• 依托单位: Institut für Organische Chemie und Makromolekulare Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2007
• 资助国家: 德国
• 起止时间: 2006-12-31 至 2014-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/35039324?language=en
• 关键词: Palladium; Catalyzed; Stereoselective; Allylic; Alkylation

The chemistry of 'hard', nonstabilized enolates and that of allylpalladium complexes was developed about the same time. Nevertheless, anionic enolates and cationic allyl complexes were not considered suitable, compatible reactants. Only during the last decade - also by contributions of our research group - the stereoselective allylic alkylation was extended to nonstabilized enolates of ketones, amides, lactams, and lactones as well as dianions of carboxylic acids, classified as particularly 'hard' nucleophiles (the latter two classes of compounds in the preceding project).Among the classic derivatives of carboxylic acids, there remain two that have - at least not in a general way - been employed in the palladium-catalyzed allylic alkylation: esters and nitriles. Filling this gap is the principle aim of the project on hand. If this goal will be reached, as indicated by our spadework, the scope and versatility of the allylic alkylation would be enhanced considerably, thus permitting to perform novel useful diastereoselective and enantioselective carbon-carbon bond formation reactions.

“硬的”、不稳定的烯醇酸盐和烯丙基钯络合物的化学几乎是在同一时间发展起来的。然而，阴离子烯醇酸盐和阳离子烯丙基络合物不被认为是合适的、相容的反应物。在过去的十年里，也是在我们的研究小组的贡献下，立体选择性的烯丙基烷基化被扩展到酮、酰胺、内酰胺和内酯的非稳定的烯醇酸盐以及羧酸的二阴离子，被归类为特别“硬”的亲核试剂(前一个项目中的后两类化合物)。在经典的羧酸衍生物中，仍然有两种-至少不是以一般的方式-用于钯催化的烯丙烷基化：酯和腈。填补这一空白是当前项目的主要目标。我们的工作表明，如果这一目标能够实现，烯丙基烷基化反应的范围和多样性将大大提高，从而可以实现新的有用的非对映选择性和对映选择性的碳-碳键形成反应。