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在无金属、无光催化剂和无光照条件下,通过芳基硼酸羟基化反应生成苯酚的可扩展实用方法。

Scalable and Practical Approach of Phenol Formation from Hydroxylation of Arylboronic Acids under Metal-, Photocatalyst-, and Light-Free Conditions.

作者信息

Cai Shuqing, Rehmat Noreen, Mahmood Zafar, Chen Qian, Huo Yanping, Ji Shaomin

机构信息

School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, P. R. China.

Guangdong Provincial Laboratory of Chemistry and Fine Chemical Engineering Jieyang Center, Jieyang 515200, P. R. China.

出版信息

ACS Omega. 2025 Jan 13;10(3):2421-2427. doi: 10.1021/acsomega.4c02844. eCollection 2025 Jan 28.

DOI:10.1021/acsomega.4c02844
PMID:39895703
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11780564/
Abstract

Phenols are of particular importance owing to their widespread application in various fields, including life sciences and synthetic chemistry. However, the typical synthetic strategies of phenol either rely on metal- or photo-catalysts or involve stringent conditions such as high temperature, strong oxidants, and acidic or basic environments. Herein, we present a remarkably simple, ecofriendly, and photocatalyst-free synthesis of phenols. In contrast to conventional methods, which relies on expensive catalysts or hazardous reagents, the current diacetoxyiodobenzene-mediated hydroxylation of arylboronic acid protocol offers significant improvement in terms of costs, operational simplicity, toxicity, and sustainability. The reaction does not require high temperature or light activation and shows good functional group compatibility and conversion efficiency (55-96%). Moreover, these mild reaction conditions are also useful for gram-scale synthesis without compromising the reaction yield.

摘要

由于酚类化合物在包括生命科学和合成化学在内的各个领域都有广泛应用,因此具有特别重要的意义。然而,酚类化合物的典型合成策略要么依赖金属催化剂或光催化剂,要么涉及高温、强氧化剂以及酸性或碱性环境等苛刻条件。在此,我们展示了一种极其简单、环保且无光催化剂的酚类化合物合成方法。与依赖昂贵催化剂或危险试剂的传统方法不同,当前通过二乙酰氧基碘苯介导的芳基硼酸羟基化方案在成本、操作简便性、毒性和可持续性方面有显著改进。该反应不需要高温或光活化,并且具有良好的官能团兼容性和转化效率(55 - 96%)。此外,这些温和的反应条件对于克级规模的合成也很有用,且不会降低反应产率。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/888a/11780564/b75c74da1907/ao4c02844_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/888a/11780564/8841add0f7f0/ao4c02844_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/888a/11780564/b75c74da1907/ao4c02844_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/888a/11780564/8841add0f7f0/ao4c02844_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/888a/11780564/b75c74da1907/ao4c02844_0002.jpg

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本文引用的文献

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Phenolic Compounds of the Medicinal Plants in an Anthropogenically Transformed Environment.人为干扰环境下药用植物的酚类化合物。
Molecules. 2023 Aug 29;28(17):6322. doi: 10.3390/molecules28176322.
2
Phenolic Compounds of L. as the Potential Alternative Therapy in the Treatment of Chronic Diseases.山黧豆中酚类化合物有望成为治疗慢性疾病的替代疗法。
Int J Mol Sci. 2023 Jul 31;24(15):12293. doi: 10.3390/ijms241512293.
3
Recent advances in oxidative phenol coupling for the total synthesis of natural products.近期在氧化酚偶联反应用于天然产物全合成方面的进展。
Nat Prod Rep. 2024 Feb 21;41(2):208-227. doi: 10.1039/d3np00009e.
4
Building a cobaloxime-based metal-organic framework for photocatalytic aerobic oxidation of arylboronic acids to phenols.构建基于钴卟啉的金属-有机框架用于芳基硼酸的光催化有氧氧化为酚类化合物。
Chem Commun (Camb). 2023 Feb 21;59(16):2239-2242. doi: 10.1039/d2cc06945h.
5
Do (Poly)phenols Matter for Nutrition Research? News from the Front.(多)酚类物质对营养研究重要吗?前沿资讯
Mol Nutr Food Res. 2022 Nov;66(21):e2200617. doi: 10.1002/mnfr.202200617.
6
An Electrochemical Method for Deborylative Hydroxylation of Arylboronic Acids under Metal-free Conditions.无金属条件下芳基硼酸的电化学去硼羟化方法。
Chem Asian J. 2022 Dec 14;17(24):e202200780. doi: 10.1002/asia.202200780. Epub 2022 Nov 14.
7
Simple and Practical Conversion of Benzoic Acids to Phenols at Room Temperature.室温下简单实用的苯甲酸到苯酚的转化。
J Am Chem Soc. 2022 Aug 31;144(34):15894-15902. doi: 10.1021/jacs.2c07529. Epub 2022 Aug 23.
8
Phenols in Pharmaceuticals: Analysis of a Recurring Motif.药物中的酚类:一个反复出现的主题的分析
J Med Chem. 2022 May 26;65(10):7044-7072. doi: 10.1021/acs.jmedchem.2c00223. Epub 2022 May 9.
9
A scalable and green one-minute synthesis of substituted phenols.一种可扩展的绿色一分钟合成取代酚的方法。
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10
Iron-catalyzed arene C-H hydroxylation.铁催化芳烃 C-H 羟化。
Science. 2021 Oct;374(6563):77-81. doi: 10.1126/science.abj0731. Epub 2021 Sep 30.