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可见光驱动的硫氰酸烯基酯的合成:用于组装多种含硫分子的新型构建模块。

Visible-light-driven synthesis of alkenyl thiocyanates: novel building blocks for assembly of diverse sulfur-containing molecules.

作者信息

Piedra Helena F, Plaza Manuel

机构信息

Departamento de Química Orgánica e Inorgánica, Instituto Universitario de Química Organometálica "Enrique Moles", Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universidad de Oviedo Julián Clavería 8 33006 Oviedo Spain

出版信息

Chem Sci. 2024 Oct 23;15(45):19077-83. doi: 10.1039/d4sc06550f.

DOI:10.1039/d4sc06550f
PMID:39483256
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11523809/
Abstract

The first visible-light-induced protocol for the general preparation of alkenyl thiocyanates from alkenyl bromides is presented. The reaction is simple, proceeds under very mild conditions and demonstrates broad functional group tolerance. Additionally, a flow protocol was developed to enable efficient scale-up of alkenyl thiocyanate synthesis, further enhancing the practicality and value of the method. Importantly, these alkenyl thiocyanates serve as valuable building blocks for the construction of diverse families of sulfur-containing molecules through trifluoromethylations, cycloadditions, oxidations, and C-S or P-S bond forming reactions.

摘要

本文介绍了首个由烯基溴化物通用制备烯基硫氰酸酯的可见光诱导反应方案。该反应简单,在非常温和的条件下进行,并具有广泛的官能团耐受性。此外,还开发了一种连续流动反应方案,以实现烯基硫氰酸酯合成的高效放大,进一步提高了该方法的实用性和价值。重要的是,这些烯基硫氰酸酯可作为有价值的结构单元,通过三氟甲基化、环加成、氧化以及碳-硫或磷-硫键形成反应,构建各种含硫分子家族。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1c34/11578243/c5c5ff72da29/d4sc06550f-s4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1c34/11578243/b6746413b7fd/d4sc06550f-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1c34/11578243/45d2785f2a93/d4sc06550f-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1c34/11578243/3b8d945a8189/d4sc06550f-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1c34/11578243/c5c5ff72da29/d4sc06550f-s4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1c34/11578243/b6746413b7fd/d4sc06550f-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1c34/11578243/45d2785f2a93/d4sc06550f-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1c34/11578243/3b8d945a8189/d4sc06550f-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1c34/11578243/c5c5ff72da29/d4sc06550f-s4.jpg

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Advancements in visible-light-induced reactions via alkenyl radical intermediates.通过烯基自由基中间体实现的可见光诱导反应的进展。
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Radical Homopolymerization of Linear α-Olefins Enabled by 1,4-Cyano Group Migration.
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Angew Chem Int Ed Engl. 2024 Jun 17;63(25):e202402511. doi: 10.1002/anie.202402511. Epub 2024 May 20.
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Continuous flow synthesis enabling reaction discovery.连续流动合成助力反应发现。
Chem Sci. 2024 Feb 28;15(13):4618-4630. doi: 10.1039/d3sc06808k. eCollection 2024 Mar 27.
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Photochemical Halogen-Bonding Promoted Synthesis of Vinyl Sulfones via Vinyl and Sulfonyl Radicals.光化学卤素键促进通过乙烯基和磺酰基自由基合成乙烯基砜
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