氧化还原无辜的钪(III)作为可见光光氧化反应的唯一催化剂

Radek, Cibulka, Amal, Tolba, Ahmed M., El-Zohry, Jafar Iqbal , Khan, Eva, Svobodová, Josef, Chudoba, Jiří, Klíma, Karol, Lušpai, Jiří, Šturala
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引用次数: 0

摘要

近年来,三氟酸钪[Sc(OTf)3]的催化活性由于其强大的刘易斯酸性和Sc3+的亲氧性而引起了人们的广泛关注。这些特征在发展各种有机反应方面取得了令人印象深刻的进展,包括C-C键的形成。Sc3+阳离子也促进光诱导反应中的单电子转移(SET)过程,或者通过配位有机光氧化还原催化剂,从而大大改变其氧化还原反应活性,或者通过从光吸收氧化还原活性化合物中转移电子后形成钪-超氧阴离子络合物(Sc3+-O-O•−)。先前认为Sc3+是一种氧化还原非活性/无害的金属离子,最初阻碍了Sc(OTf)3作为唯一可见光光氧化还原催化剂的可能性的研究。这项研究开辟了新的领域,首次展示了Sc(OTf)3作为可见光催化剂的使用,它能够通过氧化苯基位置和直接氰化芳环来直接和温和地氧化芳基物的C-H功能化。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Redox-innocent scandium(III) as the sole catalyst in visible light photooxidations
In recent years, the catalytic activity of scandium triflate [Sc(OTf)3] has attracted significant attention due to its robust Lewis acidity and the oxophilicity of Sc3+. These features have led to impressive progress in developing diverse organic reactions, including C-C bond formation. The Sc3+ cation also facilitates single electron transfer (SET) processes in photoinduced reactions either by coordination to an organophotoredox catalyst, which substantially modifies its redox reactivity, or by the formation of a scandium–superoxide anion complex (Sc3+-O-O•−) after electron transfer from a light-absorbing redox-active compound. The prior consideration of Sc3+ as a redox-inactive/innocent metal ion initially hampered the investigation of the possibility of using Sc(OTf)3 as a sole visible light photoredox catalyst. This research breaks new ground by demonstrating the inaugural use of Sc(OTf)3 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.
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