Pd-catalyzed Mizoroki–Heck reactions using cyclohexenone and related cyclic enones are surprisingly difficult, contrasting related reactions with acyclic-conjugated alkenes. In this report, we uncover several challenges associated with the reaction, including the decomposition of the starting materials and products during the reaction. Kinetic analysis, reaction optimization, and stoichiometric studies reveal the mechanistic origin of these challenges, and a catalyst system featuring BippyPhos as a ligand and TMP as a base is shown to promote successful reactions with a range of (hetero)aryl bromide coupling partners.

中文翻译：

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理解和控制环烯酮的 Mizoroki-Heck 反应


与无环共轭烯烃的相关反应相比，使用环己烯酮和相关环烯酮的 Pd 催化 Mizoroki-Heck 反应出人意料地困难。在本报告中，我们揭示了与反应相关的几个挑战，包括反应过程中起始材料和产物的分解。动力学分析、反应优化和化学计量研究揭示了这些挑战的机理根源，并且以 BippyPhos 作为配体和 TMP 作为碱的催化剂系统被证明可以促进与一系列（杂）芳基溴偶联伙伴的成功反应。