Enantioselective Catalysis of an Anionic Oxy‐Cope Rearrangement Enabled by Synergistic Ion Binding,Israel Journal of Chemistry

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Enantioselective Catalysis of an Anionic Oxy‐Cope Rearrangement Enabled by Synergistic Ion Binding
Israel Journal of Chemistry ( IF 2.3 ) Pub Date : 2020-03-06 , DOI: 10.1002/ijch.201900168
C Rose Kennedy ₁ , Bo Young Choi ₁ , Mary-Grace R Reeves ₁ , Eric N Jacobsen ₁

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Charge‐accelerated rearrangements present interesting challenges to enantioselective catalysis, due in large part to the competing requirements for maximizing reactivity (ion‐pair separation) and stereochemical communication. Herein, we describe application of a synergistic ion‐binding strategy to catalyze the anionic oxy‐Cope rearrangement of a symmetric bis‐styrenyl allyl alcohol in up to 75 : 25 e.r. Structure‐reactivity‐selectivity relationship studies, including linear free‐energy‐relationship analyses, with bifunctional urea catalysts indicate that H‐bonding and cation‐binding interactions act cooperatively to promote the chemo‐ and enantioselective [3,3]‐rearrangement. Implications for catalyst designs applicable to other transformations involving oxyanionic intermediates are discussed.

中文翻译：

通过协同离子结合实现阴离子 Oxy-Cope 重排的对映选择性催化

电荷加速重排对对映选择性催化提出了有趣的挑战，这在很大程度上是由于最大化反应性（离子对分离）和立体化学通讯的竞争要求。在此，我们描述了在高达 75 : 25 er 的结构-反应性-选择性关系研究中应用协同离子结合策略来催化对称双苯乙烯基烯丙醇的阴离子 oxy-Cope 重排，包括线性自由能关系双功能尿素催化剂的分析表明，氢键和阳离子结合相互作用共同促进化学和对映选择性[3,3]重排。讨论了适用于涉及含氧阴离子中间体的其他转化的催化剂设计的含义。

更新日期：2020-03-06

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