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Carbonylative cycloaddition of alkenes and imines to β-lactams enabled by resolving the acid-base paradox
Chem Catalysis Pub Date : 2022-05-18 , DOI: 10.1016/j.checat.2022.04.021
Yongzheng Ding , Hanmin Huang

Catalytic carbonylative cycloaddition of alkenes and imines is an ideal and unprecedented transformation for the synthesis of β-lactams; however, such a process remains largely elusive and presents onerous challenge. The main hurdle is basically due to the acid-base paradox imparted by the proton-addition and -elimination elementary steps required in the catalytic process. We report herein a strategy to resolve the acid-base paradox by identifying an appropriate basic solvent, which can accommodate both acid and base for sustaining the palladium catalysis. Such a strategy enabled an efficient Pd-catalyzed hydrocarbonylative cycloaddition reaction, which can transfer a wide variety of electron-deficient alkenes, dienes, cyclic alkenes, styrenes, and imines in the presence of CO into a large set of nitrile-containing, allylic, and spirocyclic β-lactams. Mechanistic studies disclosed that this success can be ascribed to the basic solvent N-methyl-2-pyrrolidone (NMP), which can sustain the generation of HPdX species in presence of acid and base.



中文翻译:

通过解决酸碱悖论实现烯烃和亚胺与 β-内酰胺的羰基环加成反应

烯烃和亚胺的催化羰基环加成是合成β-内酰胺的理想且前所未有的转化;然而,这样一个过程在很大程度上仍然难以捉摸,并提出了艰巨的挑战。主要障碍基本上是由于催化过程中所需的质子加成和消除基本步骤所带来的酸碱悖论。我们在此报告了一种通过确定合适的碱性溶剂来解决酸碱悖论的策略,该溶剂可以同时容纳酸和碱以维持钯催化。这种策略实现了高效的 Pd 催化的烃基环加成反应,该反应可以在 CO 存在下将多种缺电子烯烃、二烯烃、环烯烃、苯乙烯和亚胺转移到大量含腈、烯丙基、和螺环β-内酰胺。机理研究表明,这种成功可归因于碱性溶剂N-甲基-2-吡咯烷酮 (NMP),它可以在酸和碱存在的情况下维持 HPdX 物种的产生。

更新日期:2022-05-18
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