使用温和的 SmI2-D2O 通过硫代酰胺的还原脱氢反应高化学选择性合成 α、α-二氘代胺

IF 4.9 1区化学 Q1 CHEMISTRY, ORGANIC Organic Letters Pub Date : 2024-10-15 DOI:10.1021/acs.orglett.4c03434

Hengzhao Li, Kemeng Wang, Wangyu Zhao, Xinxin Li, Yijing Fu, Hainam Do, Jie An, Zhaonong Hu

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引用次数: 0

摘要

本研究报道了一种利用 SmI2 和 D2O 对硫代酰胺进行单电子转移（SET）还原脱氢反应的高效化学选择性方案。该方法通过硫代酮基中间体生成α,α-二氚基胺，不会产生醇类副产物，与酰胺的 SET 还原反应不同。硫代酰胺固有的高反应活性使其无需使用 Et3N 等配体来提高 SmI2 的还原能力，从而使反应条件更为温和，可兼容多种敏感官能团。该方案可容忍伯、仲脂肪族和芳香族硫代酰胺，从而合成出 27 种 α,α-二氘代胺和有价值的氘代氮杂环，氘合率高达 95%。

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Highly Chemoselective Synthesis of α, α-Dideuterio Amines by the Reductive Deuteration of Thioamides Using Mild SmI2–D2O

An efficient and chemoselective protocol for the single-electron-transfer (SET) reductive deuteration of thioamides using SmI₂ and D₂O 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 Et₃N to improve the reducing power of SmI₂, 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.

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来源期刊

Organic Letters 化学-有机化学

CiteScore

9.30

自引率

11.50%

发文量

1607

审稿时长

1.5 months

期刊介绍： Organic Letters invites original reports of fundamental research in all branches of the theory and practice of organic, physical organic, organometallic,medicinal, and bioorganic chemistry. Organic Letters provides rapid disclosure of the key elements of significant studies that are of interest to a large portion of the organic community. In selecting manuscripts for publication, the Editors place emphasis on the originality, quality and wide interest of the work. Authors should provide enough background information to place the new disclosure in context and to justify the rapid publication format. Back-to-back Letters will be considered. Full details should be reserved for an Article, which should appear in due course.