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电子供体-受体络合物驱动的无光催化剂合成硝基环丙烷。

Electron donor-acceptor complex-driven photocatalyst-free synthesis of nitrocyclopropanes.

作者信息

Pérez-Ramos Paula, Godinho Patrícia I C, Soengas Raquel G, Rodríguez-Solla Humberto

机构信息

Department of Organic and Inorganic Chemistry, Instituto Universitario de Química Organometálica Enrique Moles, University of Oviedo Julián Clavería 8 33006 Oviedo Spain

出版信息

RSC Adv. 2025 May 8;15(19):15155-15163. doi: 10.1039/d5ra02540k. eCollection 2025 May 6.

DOI:10.1039/d5ra02540k
PMID:40343315
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12060227/
Abstract

Herein, a visible light-promoted metal-free protocol for the synthesis of nitrocyclopropanes under mild conditions is reported. Specifically, the process is driven by the photochemical activity of ternary EDA complexes formed upon complexation of α-bromonitrostyrenes and DIPEA in the presence of benzaldehyde. This reaction provides a variety of densely functionalized cyclopropanes with good selectivity under mild reaction conditions. Mechanistic investigations on the aspects of the process also demonstrate formation of the hypothesized EDA complex.

摘要

本文报道了一种在温和条件下可见光促进的无金属合成硝基环丙烷的方法。具体而言,该过程由α-溴硝基苯乙烯与二异丙基乙胺(DIPEA)在苯甲醛存在下络合形成的三元电子给体-受体(EDA)络合物的光化学活性驱动。该反应在温和的反应条件下提供了多种具有良好选择性的高度官能化环丙烷。对该过程各方面的机理研究也证实了假设的EDA络合物的形成。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b531/12060227/5c2148f32b40/d5ra02540k-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b531/12060227/623efc7c82d3/d5ra02540k-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b531/12060227/515b604372b6/d5ra02540k-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b531/12060227/5c2148f32b40/d5ra02540k-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b531/12060227/623efc7c82d3/d5ra02540k-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b531/12060227/515b604372b6/d5ra02540k-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b531/12060227/5c2148f32b40/d5ra02540k-s3.jpg

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J Org Chem. 2025 Feb 28;90(8):2842-2847. doi: 10.1021/acs.joc.4c02177. Epub 2025 Feb 13.
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Visible-light-driven synthesis of alkenyl thiocyanates: novel building blocks for assembly of diverse sulfur-containing molecules.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。
Chem Sci. 2024 Oct 23;15(45):19077-83. doi: 10.1039/d4sc06550f.
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Synthesis of β-enamino malonates through caesium carbonate-promoted reaction of nitro-substituted donor-acceptor cyclopropanes.
通过碳酸铯促进硝基取代的给体-受体环丙烷反应合成β-烯氨基丙二酸酯。
RSC Adv. 2024 Oct 22;14(45):33587-33591. doi: 10.1039/d4ra05619a. eCollection 2024 Oct 17.
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Facile Access to Terminal Nitroalkanes via Anti-Markovnikov Hydronitration and Hydronitroalkylation of Alkenes Using Photoredox Catalysis.通过光氧化还原催化实现烯烃的反马氏氢硝化和氢硝基烷基化反应,简便合成末端硝基烷烃。
Chemistry. 2024 Dec 13;30(70):e202403654. doi: 10.1002/chem.202403654. Epub 2024 Nov 6.
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