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

“硬”，不稳定的烯醇化物和烯丙基钯配合物的化学大约在同一时间发展。然而，阴离子烯醇化物和阳离子烯丙基络合物不被认为是合适的、相容的反应物。只有在过去的十年中-也是通过我们的研究小组的贡献-立体选择性烯丙基烷基化才扩展到酮，酰胺，内酰胺和内酯的不稳定烯醇化物以及羧酸的二价阴离子，归类为特别'硬'亲核试剂（前一项目中的后两类化合物）。在羧酸的经典衍生物中，仍然有两种--至少不是以通常的方式--用于钯催化的烯丙基烷基化：酯和腈。填补这一空白是本项目的主要目标。如果这一目标将达到，如我们的前期工作所示，烯丙基烷基化的范围和通用性将大大增强，从而允许进行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。

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.