热烈祝贺课题组博士研究生成轩题为“Simple and Versatile Nitrooxylation: Noncyclic Hypervalent Iodine Nitrooxylating Reagent”的论文被Angewandte Chemie International Edition接收

中文标题：一种简单通用的非环高价碘硝酸酯化试剂

英文标题：Simple and Versatile Nitrooxylation: Noncyclic Hypervalent Iodine Nitrooxylating Reagent

刊物名称及期号、页码：Angew. Chem. Int. Ed.  2023, e.202302521.

作者姓名（中文）：成轩，殷权，蒋宇轩，江岭峰，李思源，程熠飞，孙心畅，彭禄军，钟成，邓清海*

作者姓名（英文）：Xuan Cheng, Quan Yin, Yu-Xuan Jiang, Ling-Feng Jiang, Si-Yuan Li, Yi-Fei Cheng, Xin-Chang Sun, Lujun Peng, Cheng Zhong, and Qing-Hai Deng*

本工作以 "Research Articles" 的形式发表在Angew. Chem. Int. Ed.上，并被评为"Hot Paper", 谨以此文怀念陆熙炎先生。

摘要（英文）：Organic nitrates are broadly applied as pharmaceuticals (acting as efficient nitric oxide donor), energetic materials, building blocks in organic synthesis, etc. However, practical and direct methods to access organic nitrates efficiently is still rare mainly due to the lack of powerful nitrooxylating reagents. Herein, we report a kind of bench-stable and highly reactive noncyclic hypervalent iodine nitrooxylating reagents, oxybis(aryl-λ³-iodanediyl) dinitrates (OAIDNs, 2), which are prepared just by using aryliodine diacetate and HNO₃. The reagents are used to achieve a mild and operationally simple protocol to access diverse organic nitrates. By employing of 2, zinc-catalyzed regioselective nitrooxylation of cyclopropyl silyl ethers is realized efficiently to offer the corresponding β-nitrooxy ketones with high functional group tolerance. Moreover, a series of direct and catalyst-free nitrooxylations of enolizable C-H bonds are carried out smoothly to afford the desired organic nitrates by just mixing the substrates with 2 in dichloromethane in minutes.

工作简介：

硝酸酯类化合物，不仅作为一氧化氮的供体，常用于心血管药物，还可以用于改善已有药物（增强药效、降低毒副作用），在医药、含能材料、有机合成砌块等领域上有着广泛的应用。目前虽然已有一些硝酸酯化反应被开发出来，但仍有很多局限和不足，主要在于：1）不可避免使用混酸体系或者当量金属试剂；2）反应选择性差、底物范围窄；3）底物需要预活化。基于绿色和可持续化学的发展理念，开发新型硝酸酯化试剂以实现高效的硝酸酯化反应是亟待解决且富有挑战性的课题。

邓清海教授课题组基于组内先前关于高价碘试剂的研究经验（Org. Chem. Front., 2016, 3, 934; Org. Lett. 2019, 21, 7315; Org. Chem. Front., 2020, 7, 3509），从廉价的二乙酸碘苯或芳基碘出发，以硝酸为原料，成功设计并合成了一类结构稳定、活性可调的硝酸酯化试剂，开发了一系列安全、绿色、高效、快捷的硝酸酯化反应。同时，利用该策略还成功将硝酸酯基团成功引入到天然产物或药物分子中。该类试剂在有机合成及药物合成上有着广阔的应用前景。

创新点：从廉价的二乙酸碘苯或芳基碘出发，以硝酸为原料，成功设计并合成了一类结构稳定、活性可调的硝酸酯化试剂，开发了一系列安全绿色高效快捷的硝酸酯化反应。

全文链接： https://doi.org/10.1002/anie.202302521