热烈祝贺课题组博士生成轩题为“Practical and regioselective halonitrooxylation of olefins to access β-halonitrates”的论文被Nature Communications接收

中文标题：实用的烯烃区域选择性卤硝酸酯化合成β-卤代硝酸酯

英文标题：Practical and regioselective halonitrooxylation of olefins to access β-halonitrates

刊物名称及期号、页码： Nat. Commun., 2024, 15, 7313.

作者姓名（中文）：成轩，殷权，程熠飞，吴少华，孙心畅，孔德意，邓清海*

作者姓名（英文）：Xuan Cheng, Quan Yin, Yi-Fei Cheng, Shao-Hua Wu, Xin-Chang Sun, De-Yi Kong & Qing-Hai Deng*

摘要（英文）：Organic nitrates, as effective donors of the signaling molecule nitric oxide, are widely applied in the pharmaceutical industry. However, practical and efficient methods for accessing organic nitrates are still scarce, and achieving high regiocontrol in unactivated alkene difunctionalization remains challenging. Here we present a simple and practical method for highly regioselective halonitrooxylation of unactivated alkenes. The approach utilizes TMSX (X: Cl, Br, or I) and oxybis(aryl-λ³-iodanediyl) dinitrates (OAIDN) as sources of halogen and nitrooxy groups, with 0.5 mol % FeCl₃ as the catalyst. Remarkably, high regioselectivity in the halonitrooxylation of aromatic alkenes can be achieved even without any catalyst. This protocol features easy scalability and excellent functional group compatibility, providing a range of β-halonitrates (127 examples, up to 99% yield, up to >20:1 rr). Notably, 2-iodoethyl nitrate, a potent synthon derived from ethylene, reacts smoothly with a variety of functional units to incorporate the nitrooxy group into the desired molecules.

工作简介：

有机硝酸酯作为一氧化氮信号分子的有效供体，广泛应用于制药行业。然而，获取有机硝酸酯的高效实用的方法却很少，实现非活化烯烃双官能化的高区域选择性控制也是一个巨大的挑战。本文发展了一种简单实用的未活化烯烃高区域选择性卤-硝酸酯化反应新方法。该方法以市售的三甲基卤硅烷（卤原子可为：氯、溴、碘）和自主研发的非环高碘硝酸酯试为卤素和硝酸酯源，仅需0.5 mol%的氯化铁作为催化剂；值得注意的是，即使没有任何催化剂，芳基烯烃的卤-硝酸酯化反应也可以实现高区域选择性。该方法具有广阔的底物适用范围和良好的官能团耐受性，共报道了127例β-卤硝酸酯类化合物（收率高达99%，区域选择性高达>20:1）。值得注意的是，一种衍生自乙烯的强效合成子——2-碘硝酸乙酯，能与多种官能团（氧-氢、氮-氢、硫-氢）顺利反应，将硝酸酯基结合到所需分子中。

创新点：发展了一种简单实用的未活化烯烃高区域选择性卤-硝酸酯化反应新方法。

全文链接：doi.org/10.1038/s41467-024-51655-5