Rhodium-Catalyzed Asymmetric Arylation of Cyclobutenone Ketals
Rhodium-Catalyzed Asymmetric Arylation of Cyclobutenone Ketals
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DOI：
10.1002/anie.202217381
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发表时间：
2023-02-17
影响因子：
16.6
通讯作者：
Fletcher, Stephen P.
中科院分区：
文献类型：
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作者：
Egea-Arrebola, David;Goetzke, F. Wieland;Fletcher, Stephen P.
复杂环丁烷是生物活性分子和天然产物的重要结构单元，但其对映选择性制备方法尚未得到广泛研究。在这项工作中，我们描述了铑催化的芳基和乙烯基硼酸环丁烯酮缩酮的对映选择性加成。该转化涉及对映选择性碳化反应，得到环丁基铑中间体，然后进行β-氧消除，得到对映富集的烯醇醚。总的来说，该加成充当Rh催化的1，4-加成至环丁烯酮的替代物。
Complex cyclobutanes are important motifs in both bioactive molecules and natural products, yet their enantioselective preparation has not been widely explored. In this work, we describe rhodium-catalyzed enantioselective additions of aryl and vinyl boronic acids to cyclobutenone ketals. This transformation involves enantioselective carbometalation to give cyclobutyl-rhodium intermediates, followed by beta-oxygen elimination to afford enantioenriched enol ethers. Overall, this addition serves as a surrogate for Rh-catalyzed 1,4-additions to cyclobutenone.