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杂环电化学合成的绿色进展。

Green advancements towards the electrochemical synthesis of heterocycles.

作者信息

Hashmi Sonia Zeba, Bareth Diksha, Dwivedi Jaya, Kishore Dharma, Alvi P A

机构信息

Department of Chemistry, Banasthali Vidyapith Banasthali-304022 Rajasthan India

Department of Physical Sciences, Banasthali Vidyapith Banasthali-304022 Rajasthan India

出版信息

RSC Adv. 2024 Jun 7;14(26):18192-18246. doi: 10.1039/d4ra02812k. eCollection 2024 Jun 6.

DOI:10.1039/d4ra02812k
PMID:38854834
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11157331/
Abstract

Heterocyclic chemistry is a large field with diverse applications in the areas of biological research and pharmaceutical advancement. Numerous initiatives have been proposed to further enhance the reaction conditions to reach these compounds without using harmful compounds. This paper focuses on the recent advances in the eco-friendly and green synthetic procedures to synthesize N-, S-, and O-heterocycles. This approach demonstrates considerable potential in accessing such compounds while circumventing the need for stoichiometric quantities of oxidizing/reducing agents or catalysts containing precious metals. Merely employing catalytic quantities of these substances proves sufficient, thereby offering an optimal means of contributing to resource efficiency. Renewable electricity plays a crucial role in generating environmentally friendly electrons (oxidant/reductant) that serve as catalysts for a series of reactions. These reactions involve the production of reactive intermediates, which in turn allow the synthesis of new chemical bonds, enabling beneficial transformations to occur. Furthermore, the utilization of metals as active catalysts in electrochemical activation has been recognized as an effective approach for achieving selective functionalization. The aim of this review was to summarize the electrochemical synthetic procedures so that the undesirable side reactions can be considerably reduced and the practical potential range of the chemical reactions can be expanded significantly.

摘要

杂环化学是一个广泛的领域,在生物研究和药物研发方面有着多样的应用。人们已经提出了许多倡议,以进一步优化反应条件,在不使用有害化合物的情况下合成这些化合物。本文重点介绍了合成含氮、硫和氧杂环化合物的环保型绿色合成方法的最新进展。这种方法在合成此类化合物方面显示出巨大潜力,同时避免了使用化学计量的氧化/还原剂或含贵金属的催化剂。仅使用催化量的这些物质就已足够,从而提供了一种提高资源效率的理想方法。可再生电力在产生作为一系列反应催化剂的环境友好型电子(氧化剂/还原剂)方面发挥着关键作用。这些反应涉及活性中间体的生成,进而能够形成新的化学键,实现有益的转化。此外,在电化学活化中使用金属作为活性催化剂已被认为是实现选择性官能化的有效方法。本综述的目的是总结电化学合成方法,以便能大幅减少不良副反应,并显著扩大化学反应的实际潜在范围。

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Chem Sci. 2020 Jul 31;11(33):8657-8670. doi: 10.1039/d0sc03578e.
6
Evolution of Earth-Abundant 3 d-Metallaelectro-Catalyzed C-H Activation: From Chelation-Assistance to C-H Functionalization without Directing Groups.地球丰富的3d金属电催化C-H活化的进展:从螯合辅助到无导向基团的C-H官能团化
Chem Rec. 2021 Sep;21(9):2430-2441. doi: 10.1002/tcr.202100096. Epub 2021 May 24.
7
Electrochemical synthesis of sulfonated benzothiophenes using 2-alkynylthioanisoles and sodium sulfinates.使用 2-炔基硫代苯甲醚和亚硫酸钠电化学合成磺化苯并噻吩。
Org Biomol Chem. 2021 May 5;19(17):3844-3849. doi: 10.1039/d1ob00079a.
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Continuous-flow electrosynthesis of selenium-substituted iminoisobenzofuran via oxidative cyclization of olefinic amides and diselenides.通过烯烃酰胺和二硒化物的氧化环化连续流动电合成硒取代的异吲哚并苯并呋喃。
Org Biomol Chem. 2021 Apr 14;19(14):3207-3212. doi: 10.1039/d1ob00236h. Epub 2021 Mar 24.
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Electrooxidative Rhodium-Catalyzed [5+2] Annulations via C-H/O-H Activations.通过C-H/O-H活化实现的电氧化铑催化[5+2]环化反应
Angew Chem Int Ed Engl. 2021 Mar 15;60(12):6419-6424. doi: 10.1002/anie.202016895. Epub 2021 Feb 8.
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Oxidant- and Catalyst-Free Synthesis of Sulfonated Benzothiophenes via Electrooxidative Tandem Cyclization.无金属氧化剂和催化剂条件下通过电化学串联环化反应合成砜基苯并噻吩。
J Org Chem. 2021 Feb 5;86(3):2593-2601. doi: 10.1021/acs.joc.0c02679. Epub 2021 Jan 11.