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单一对映体螺旋桨状多核配合物作为迈克尔加成反应中对映体诱导的催化剂——概念验证

Single enantiomer propeller-shaped polynuclear complexes as catalysts-proof-of-concept for enantioinduction in a Michael addition reaction.

作者信息

Maddocks Joe, Mahesh Mohan, Sampani Stavroula I, Dixon Alexander C, Nielsen Christian D-T, Kumar Prashant, Akien Geoffrey R, Spencer John, Abdul-Sada Alaa, Turner John F C, Spivey Alan C, Kostakis George E

机构信息

Department of Chemistry, University of Sussex, Brighton, UK.

Department of Chemistry, Imperial College London, London, UK.

出版信息

R Soc Open Sci. 2025 Mar 27;12(3):241537. doi: 10.1098/rsos.241537. eCollection 2025 Mar.

Abstract

We report a family of propeller-shaped polynuclear metal complexes whose overall chirality is dictated by a single stereogenic centre within their component amino alcohol-ligand. These topologically intriguing complexes are readily prepared in enantiomerically pure form and are shown here to catalyse the conjugate addition of barbituric acids and their derivatives to nitroalkenes, with a catalyst loading of 1 mol%. Although only low levels of enantioinduction are observed, control experiments indicate that the enantioselectivity is dictated by the overall topology of the complex and not governed by binding to the tetrametallic entity, heralding a potentially new mode of catalysis.

摘要

我们报道了一类螺旋桨形状的多核金属配合物,其整体手性由其组成的氨基醇配体中的单个立体ogenic中心决定。这些拓扑结构引人入胜的配合物很容易以对映体纯形式制备,并且在此显示出能催化巴比妥酸及其衍生物与硝基烯烃的共轭加成反应,催化剂负载量为1摩尔%。虽然仅观察到低水平的对映体诱导,但对照实验表明对映选择性由配合物的整体拓扑结构决定,而非由与四金属实体的结合所控制,这预示着一种潜在的新催化模式。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ae1d/11947762/ca42cd2a6fc9/rsos.241537.f001.jpg

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