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铑催化的环丁烯酮缩酮不对称芳基化反应。

Rhodium-Catalyzed Asymmetric Arylation of Cyclobutenone Ketals.

机构信息

Department of Chemistry, Chemistry Research Laboratory, Department of Chemistry, University of Oxford, 12 Mansfield Road, Oxford, OX1 3TA, UK.

出版信息

Angew Chem Int Ed Engl. 2023 Mar 20;62(13):e202217381. doi: 10.1002/anie.202217381. Epub 2023 Feb 17.

Abstract

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 β-oxygen elimination to afford enantioenriched enol ethers. Overall, this addition serves as a surrogate for Rh-catalyzed 1,4-additions to cyclobutenone.

摘要

稠合环丁烷是生物活性分子和天然产物中的重要结构单元,但它们的对映选择性制备尚未得到广泛探索。在这项工作中,我们描述了铑催化的芳基和乙烯基硼酸对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金属化生成环丁基-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,该加成反应可作为铑催化的环丁烯酮 1,4-加成的替代方法。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0ca4/10946970/a4c0af9b6340/ANIE-62-0-g007.jpg

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