Brønsted酸通过1,4-基团迁移伴随的自由基-极性交叉实现了非应变C-C键的无金属远程氧化和酰胺化

IF 4.6 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Chemistry Frontiers Pub Date : 2025-05-14 DOI:10.1039/d5qo00549c

Xiaofei Xie, yun Shi, Yukun Li, Jinge Gui, Yingguang Zhu, Kang Chen

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引用次数: 0

摘要

碳碳键功能化已成为有机分子骨架编辑的有力工具。然而，在非环分子中通过非应变C - C键裂解形成远端C(sp3) -O和C(sp3) -N键仍然是一个挑战。在本研究中，通过1,4基团迁移和自由基-极性交叉，建立了一种Brønsted酸使NHPI酯无金属远端氧化和酰胺化的方法，以中高收率获得了各种杂芳基系链醇、醚和酰胺。该协议还具有条件温和、功能基耐受性好、区域选择性高的特点，为通过C - C键激活远程构建C(sp3) -杂原子键提供了一种新的范例。

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Brønsted acid enabled metal-free remote oxygenation and amidation of unstrained C–C bonds via 1,4-group migration chaperoned radical-polar crossover

C–C bond functionalization has emerged as a powerful tool for the skeleton editing of organic molecules. However, remote C(sp3)–O and C(sp3)–N bonds formation via unstrained C–C bond cleavage in acyclic molecules still remains challenging. Herein in this work, a Brønsted acid enabled metal-free remote oxygenation and amidation of NHPI esters via 1,4-group migration chaperoned radical-polar crossover has been established, affording a variety of heteroaryl-tethered alcohols, ethers and amides in moderate to good yields. This protocol also features mild conditions, good functional group tolerance and high regioselectivity, proving a novel paradigm for remote C(sp3)–heteroatom bond construction via C–C bond activation.

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来源期刊

Organic Chemistry Frontiers CHEMISTRY, ORGANIC-

CiteScore

7.90

自引率

11.10%

发文量

686

审稿时长

1 months

期刊介绍： Organic Chemistry Frontiers is an esteemed journal that publishes high-quality research across the field of organic chemistry. It places a significant emphasis on studies that contribute substantially to the field by introducing new or significantly improved protocols and methodologies. The journal covers a wide array of topics which include, but are not limited to, organic synthesis, the development of synthetic methodologies, catalysis, natural products, functional organic materials, supramolecular and macromolecular chemistry, as well as physical and computational organic chemistry.