Singlet Oxygen-Mediated Regioselective Thiocyanation of Terminal Alkynes, Alkenes, Indoles, Pyrrole, Anilines, and Phenols

IF 7.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

ACS Sustainable Chemistry & Engineering Pub Date : 2024-10-20 DOI:10.1021/acssuschemeng.4c05654

Mahima Gupta, Vaibhav Pramod Charpe, Kuo Chu Hwang

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引用次数: 0

Abstract

We have developed a singlet oxygen (¹O₂)-mediated regioselective thiocyanation of terminal alkynes, indoles, pyrrole, anilines, and phenols using ammonium thiocyanate (NH₄SCN) as an SCN source under visible light irradiation at room temperature. The oxidative thiocyanation of terminal alkynes forms α-keto thiocyanates, while indoles, pyrrole, anilines, and phenols regioselectively form the respective thiocyanate products. Herein, thiocyanate (SCN anion) undergoes single electron transfer (SET) by transferring an electron to singlet oxygen and forms an ^•SCN radical, which readily reacts with substrates to form thiocyanate products. Green chemistry metrics and Eco-scale evaluations signify that the current oxidative and regioselective thiocyanation protocol is an acceptable green organic synthesis process. Moreover, this method requires a simple reaction setup and uses inexpensive NH₄SCN as an SCN source, O₂ as an oxidant, and low-energy visible light. Thus, the current oxidative thiocyanation process is mild, green, highly efficient, eco-friendly, and environmentally feasible.

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单线态氧介导的末端炔烃、烯烃、吲哚、吡咯、苯胺和酚的区域选择性硫氰酸化反应

我们开发了一种单线态氧（1O2）介导的顶端炔烃、吲哚、吡咯、苯胺和酚的区域选择性硫氰化反应，该反应以硫氰酸铵（NH4SCN）为 SCN 源，在室温可见光照射下进行。末端炔烃的氧化硫氰酸化会形成 α-酮硫氰酸盐，而吲哚、吡咯、苯胺和酚则会选择性地形成相应的硫氰酸盐产物。在这里，硫氰酸盐（SCN 阴离子）通过将一个电子转移到单线态氧来进行单电子转移 (SET)，并形成一个 -SCN 自由基，该自由基很容易与底物反应生成硫氰酸盐产物。绿色化学指标和生态规模评估表明，目前的氧化和区域选择性硫氰酸化方案是一种可接受的绿色有机合成工艺。此外，该方法只需一个简单的反应装置，并使用廉价的 NH4SCN 作为 SCN 源、O2 作为氧化剂以及低能量的可见光。因此，目前的氧化硫氰酸化工艺是温和、绿色、高效、生态友好和环境可行的。

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来源期刊

ACS Sustainable Chemistry & Engineering CHEMISTRY, MULTIDISCIPLINARY-ENGINEERING, CHEMICAL

CiteScore

13.80

自引率

4.80%

发文量

1470

审稿时长

1.7 months

期刊介绍： ACS Sustainable Chemistry & Engineering is a prestigious weekly peer-reviewed scientific journal published by the American Chemical Society. Dedicated to advancing the principles of green chemistry and green engineering, it covers a wide array of research topics including green chemistry, green engineering, biomass, alternative energy, and life cycle assessment. The journal welcomes submissions in various formats, including Letters, Articles, Features, and Perspectives (Reviews), that address the challenges of sustainability in the chemical enterprise and contribute to the advancement of sustainable practices. Join us in shaping the future of sustainable chemistry and engineering.