Lopat'eva Elena R, Krylov Igor B, Paveliev Stanislav A, Emtsov Daniil A, Kostyagina Vera A, Korlyukov Alexander A, Terent'ev Alexander O
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prospekt, 119991 Moscow, Russia.
D. I. Mendeleev University of Chemical Technology of Russia, 9 Miusskaya Square, 125047 Moscow, Russia.
J Org Chem. 2023 Sep 15;88(18):13225-13235. doi: 10.1021/acs.joc.3c01470. Epub 2023 Aug 24.
The selective successive addition of azide (•N) and -oxyl radicals to alkenes is demonstrated, despite each of the two radicals being known to attack C═C bonds and the mixture of radical adducts possibly being expected. The proposed radical mechanism was supported by density functional theory calculations, electron paramagnetic resonance, and radical trapping experiments. The reaction proceeds at room temperature with the available reagents: NaN, -hydroxy compounds, and PhI(OAc) as the oxidant. The method can be applied for -hydroxyimides, -hydroxyamides, -hydroxybenzotriazole, and oximes as -oxyl radical precursors. Vinylarenes, aliphatic alkenes, and even electron-deficient methyl methacrylate were successfully functionalized.
尽管已知叠氮自由基（•N）和-氧基自由基都会进攻碳碳双键，且可能会生成自由基加合物混合物，但仍证明了它们能选择性地依次加成到烯烃上。所提出的自由基机理得到了密度泛函理论计算、电子顺磁共振和自由基捕获实验的支持。该反应在室温下使用现有的试剂（NaN、-羟基化合物和作为氧化剂的PhI(OAc)）即可进行。该方法可用于将-羟基酰亚胺、-羟基酰胺、-羟基苯并三唑和肟作为-氧基自由基前体。乙烯基芳烃、脂肪族烯烃，甚至缺电子的甲基丙烯酸甲酯都成功实现了官能化。
