使用温和的SmI-DO通过硫代酰胺的还原氘代反应高度化学选择性合成α,α-二氘代胺
Highly Chemoselective Synthesis of α, α-Dideuterio Amines by the Reductive Deuteration of Thioamides Using Mild SmI-DO.
作者信息
Li Hengzhao, Wang Kemeng, Zhao Wangyu, Li Xinxin, Fu Yijing, Do Hainam, An Jie, Hu Zhaonong
机构信息
Key Laboratory of Plant Protection Resources and Pest Management of Ministry of Education, Key Laboratory of Integrated Pest Management on the Loess Plateau of Ministry of Agriculture and Rural Affairs, College of Plant Protection, Northwest A&F University, Yangling 712100, Shaanxi, China.
Key Laboratory for Botanical Pesticide R&D of Shaanxi Province, Yangling 712100, Shaanxi, China.
出版信息
Org Lett. 2024 Oct 25;26(42):9120-9125. doi: 10.1021/acs.orglett.4c03434. Epub 2024 Oct 15.
An efficient and chemoselective protocol for the single-electron-transfer (SET) reductive deuteration of thioamides using SmI and DO is reported. This method uniquely produces α,α-dideuterio amines via a thio-ketyl radical intermediate without generating alcohol byproducts, distinguishing it from the SET reduction of amides. The inherent high reactivity of thioamides obviates the need for ligands like EtN to improve the reducing power of SmI, thereby enabling milder reaction conditions that are compatible with a broad range of sensitive functional groups. This protocol tolerates both primary and secondary aliphatic and aromatic thioamides, leading to the synthesis of 27 α,α-dideuterio amines and valuable deuterated nitrogen heterocycles with >95% deuterium incorporations.
报道了一种使用SmI₂和D₂O进行硫代酰胺单电子转移（SET）还原氘代的高效且化学选择性的方法。该方法通过硫代酮基自由基中间体独特地生成α,α-二氘代胺，且不产生醇副产物，这使其有别于酰胺的SET还原。硫代酰胺固有的高反应活性消除了对诸如Et₃N等配体的需求，以提高SmI₂的还原能力，从而实现与多种敏感官能团兼容的更温和反应条件。该方法适用于伯、仲脂肪族和芳香族硫代酰胺，可合成27种α,α-二氘代胺和氘掺入率>95%的有价值的氘代氮杂环化合物。
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