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无氧化还原活性的钪(III)作为可见光光氧化反应中的唯一催化剂。

Redox-innocent scandium(III) as the sole catalyst in visible light photooxidations.

作者信息

Tolba Amal Hassan, El-Zohry Ahmed M, Khan Jafar Iqbal, Svobodová Eva, Chudoba Josef, Klíma Jiří, Lušpai Karol, Pižl Martin, Šturala Jiří, Cibulka Radek

机构信息

Department of Organic Chemistry, University of Chemistry and Technology, Prague, Prague, 166 28, Czech Republic.

Chemistry Department, Faculty of Science, Assiut University, Assiut, 71515, Egypt.

出版信息

Nat Commun. 2025 Aug 22;16(1):7851. doi: 10.1038/s41467-025-63233-4.

Abstract

In recent years, the catalytic activity of scandium triflate Sc(OTf) has attracted significant attention due to its robust Lewis acidity and the oxophilicity of Sc. These features have led to impressive progress in developing diverse organic reactions, including C-C bond formation. The Sc also facilitates single electron transfer in photoinduced reactions either by coordination to an organophotoredox catalyst, which modifies its redox reactivity, or by the formation of a scandium-superoxide anion complex after electron transfer from a light-absorbing redox-active compound. The prior consideration of Sc as a redox-inactive/innocent metal ion initially hampered the investigation of the possibility of using Sc(OTf) as a sole visible light photoredox catalyst. This work demonstrates the use of Sc(OTf) as a visible light photocatalyst capable of direct and mild aerobic oxidative C-H functionalisation of aromatic substrates by oxidation of the benzylic position and direct cyanation of the aromatic ring.

摘要

近年来,三氟甲磺酸钪(Sc(OTf))的催化活性因其强大的路易斯酸性和钪的亲氧性而备受关注。这些特性在开发包括碳-碳键形成在内的各种有机反应方面取得了令人瞩目的进展。钪还通过与有机光氧化还原催化剂配位(这会改变其氧化还原反应活性)或在光吸收性氧化还原活性化合物发生电子转移后形成钪-超氧阴离子络合物,从而促进光诱导反应中的单电子转移。先前将钪视为氧化还原惰性/无害金属离子的观念最初阻碍了对使用Sc(OTf)作为唯一可见光光氧化还原催化剂可能性的研究。这项工作展示了Sc(OTf)作为一种可见光光催化剂的用途,它能够通过苄基位置的氧化和芳环的直接氰化,对芳香底物进行直接且温和的需氧氧化C-H官能化反应。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2a81/12373787/f850d3c5da87/41467_2025_63233_Fig1_HTML.jpg

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