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配体促进的有机卤化物的金催化氰化反应

Ligand-Enabled Gold-Catalyzed Cyanation of Organohalides.

作者信息

Kumar Anil, Bhattacharya Nandita, Mane Manoj V, Patil Nitin T

机构信息

Department of Chemistry, Indian Institute of Science Education and Research Bhopal, Bhopal Bypass Road, Bhauri, Bhopal, 462 066, India.

Centre for Nano and Material Sciences, Jain (Deemed-to-be University), Jain Global Campus Kanakapura, Bangalore, Karnataka, 562112, India.

出版信息

Angew Chem Int Ed Engl. 2024 Nov 18;63(47):e202412682. doi: 10.1002/anie.202412682. Epub 2024 Oct 14.

Abstract

Herein, we disclose the first report on gold-catalyzed C(sp)-CN cross-coupling reaction by employing a ligand-enabled Au(I)/Au(III) redox catalysis. This transformation utilizes acetone cyanohydrin as a nucleophilic cyanide source to convert simple aryl and alkenyl iodides into the corresponding nitriles. Combined experimental and computational studies highlighted the crucial role of cationic silver salts in activating the stable (P,N)-AuCN complex towards the oxidative addition of aryl iodides to subsequently generate key aryl-Au(III) cyanide complexes.

摘要

在此,我们首次报道了通过配体促进的金(I)/金(III)氧化还原催化实现的金催化C(sp)-CN交叉偶联反应。该转化利用丙酮氰醇作为亲核氰化物源,将简单的芳基和烯基碘化物转化为相应的腈。结合实验和计算研究突出了阳离子银盐在活化稳定的(P,N)-AuCN络合物以促进芳基碘化物的氧化加成从而随后生成关键的芳基-金(III)氰化物络合物方面的关键作用。

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