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双光化学 H-原子转移和钴催化从环己酮制备不饱和酚的反应。

Dual Photochemical H-Atom Transfer and Cobalt Catalysis for the Desaturative Synthesis of Phenols from Cyclohexanones.

作者信息

Caldora Henry P, Zhang Zhenhua, Tilby Michael J, Turner Oliver, Leonori Daniele

机构信息

Department of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, UK.

Oncology R&DI Medicinal Chemistry, AstraZeneca Darwin Building, Unit 310, Cambridge Science Park, Milton Road, Cambridge, CB4 0WG, UK.

出版信息

Angew Chem Int Ed Engl. 2023 Jun 19;62(25):e202301656. doi: 10.1002/anie.202301656. Epub 2023 May 9.

Abstract

Phenols are integral aromatic molecules widely encountered in the structure of natural products and routinely utilised for the synthesis of high-value materials. Accessing highly substituted derivatives can often be difficult, especially when their functionalization pattern does not match the intrinsic reactivity leveraged by electrophilic aromatic substitution (S Ar) chemistry. Here, we provide an alternative and mechanistically distinct approach for phenol synthesis using saturated cyclohexanone precursors. This process operates at ambient temperature, under simple purple light irradiation, and features a dual catalytic manifold carrying four sequential H-atom transfer processes.

摘要

酚类是天然产物结构中常见的基本芳香分子,通常用于合成高价值材料。获得高度取代的衍生物通常很困难,尤其是当它们的功能化模式与亲电芳香取代(S Ar)化学所利用的固有反应性不匹配时。在这里,我们提供了一种使用饱和环己酮前体合成苯酚的替代且在机理上不同的方法。该过程在环境温度下,在简单的紫光照射下进行,并采用具有四个连续 H 原子转移过程的双催化机制。

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