Kesharwani Tanay, Verma Akhilesh K, Emrich Daniel, Ward Jeffrey A, Larock Richard C
Department of Chemistry, Iowa State University, Ames, Iowa 50011, USA.
Org Lett. 2009 Jun 18;11(12):2591-3. doi: 10.1021/ol900940k.
Examples of the 1,4-migration of a palladium moiety in aryl- and alkylpalladium intermediates to the acyl position of an aldehyde or formamide have been observed. The resulting acylpalladium intermediate can undergo ester or carbamate formation by reaction with an alcohol; decarbonylation, followed by beta hydride elimination to an alkene; reaction with an organomercurial to form an ester; or alkene insertion. Deuterium-labeling studies have been used to confirm the palladium migration mechanism.
已观察到芳基钯和烷基钯中间体中钯部分向醛或甲酰胺的酰基位置进行1,4-迁移的实例。生成的酰基钯中间体可通过与醇反应形成酯或氨基甲酸酯；脱羰基，随后β-氢消除生成烯烃；与有机汞化合物反应形成酯；或进行烯烃插入反应。氘标记研究已用于证实钯的迁移机制。
