Fenton Chemistry for Achmatowicz Rearrangement,ACS Catalysis

当前位置： X-MOL 学术 › ACS Catal. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Fenton Chemistry for Achmatowicz Rearrangement
ACS Catalysis ( IF 11.3 ) Pub Date : 2021-03-09 , DOI: 10.1021/acscatal.1c00219
Guodong Zhao ₁ , Lixin Liang , Eryu Wang , Rongbiao Tong ₂

Affiliation

Achmatowicz rearrangement (AchR) is a very important transformation for the synthesis of various heterocyclic building blocks and natural products. Here, the discovery of Fenton chemistry for AchR using a bifunctional catalyst (FeBr₂ or CeBr₃), which has environmental friendliness and a broad substrate scope at the same time has been reported. This method addresses the major limitation of conventional chemical (hazardous) and enzymatic (limited scope) methods. Mechanistic studies suggested that reactive brominating species (RBS) is the true catalyst for AchR and that Fenton chemistry [Fe/Ce (cat.) + H₂O₂ → HO^•/HOO^• + H₂O] is responsible for the oxidation of bromide into RBS. Importantly, this in situ RBS generation from M-Br_x–H₂O₂ under neutral conditions addresses the long-lasting problem of many haloperoxidase mimics that require a strong acidic additive/medium for bromide oxidation with H₂O₂, which creates opportunities for many other brominium-mediated organic reactions.

中文翻译：

Fenton化学用于Achmatowicz重排

Achmatowicz重排（AchR）是合成各种杂环结构单元和天然产物的非常重要的转变。在此，已经报道了使用具有环境友好性并且同时具有广泛的底物范围的双功能催化剂（FeBr ₂或CeBr ₃）对AchR的芬顿化学的发现。该方法解决了常规化学（危险）和酶促（有限范围）方法的主要局限性。机理研究表明，反应性溴化物种（RBS）是AchR的真正催化剂，Fenton化学[Fe / Ce（cat。）+ H ₂ O ₂ →HO ^• / HOO ^• + H ₂O]负责将溴化物氧化为RBS。重要的是，这种在中性条件下由M-Br _x -H ₂ O ₂生成的原位RBS解决了许多卤代过氧化物酶模拟物的长期存在的问题，这些模拟物需要强酸性添加剂/介质来与H ₂ O ₂进行溴化物氧化，这创造了机会用于许多其他溴介导的有机反应。

更新日期：2021-03-19

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南