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直接从羧酸和有机卤化物升级酮合成。

Upgrading ketone synthesis direct from carboxylic acids and organohalides.

作者信息

Ruzi Rehanguli, Liu Kai, Zhu Chengjian, Xie Jin

机构信息

State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China.

College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou, 450001, China.

出版信息

Nat Commun. 2020 Jul 3;11(1):3312. doi: 10.1038/s41467-020-17224-2.

Abstract

The ketone functional group has a unique reactivity in organic chemistry and is associated with a number of useful reactions. Catalytic methods for ketone synthesis are continually being developed. Here, we report a photoredox, nickel and phosphoranyl radical synergistic cross-electrophile coupling of commercially available chemicals, aromatic acids and aryl/alkyl bromides. This allows for concise synthesis of highly functionalized ketones directly, without the preparation of activated carbonyl intermediates or organometallic compounds, and thus complements the conventional Weinreb ketone synthesis. Use of the appropriate photocatalyst, ligand amount and solvents can match the reaction rate required by any simple catalytic cycle. The practicality and synthetic robustness of the reaction are illustrated by the facile synthesis of complex ketones from readily available feedstock chemicals.

摘要

酮官能团在有机化学中具有独特的反应活性,并与许多有用的反应相关。酮合成的催化方法不断得到发展。在此,我们报道了一种光氧化还原、镍和膦基自由基协同的市售化学品、芳香酸与芳基/烷基溴的交叉亲电偶联反应。这使得直接简洁地合成高度官能化的酮成为可能,无需制备活性羰基中间体或有机金属化合物,从而补充了传统的温勒伯酮合成方法。使用合适的光催化剂、配体用量和溶剂可以匹配任何简单催化循环所需的反应速率。由易得的原料化学品轻松合成复杂酮,说明了该反应的实用性和合成稳健性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9da7/7334210/d4b6c26230e9/41467_2020_17224_Fig1_HTML.jpg

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