Photocatalytic furan-to-pyrrole conversion

• 成果类型: Article
• 署名作者: Kim, Donghyeon; You, Jaehyun; Lee, Da Hye; Hong, Hojin; Kim, Dongwook; Park, Yoonsu
• 署名单位: Korea Advanced Institute of Science & Technology (KAIST); Institute for Basic Science - Korea (IBS)
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-11606
• DOI: 10.1126/science.adq6245
• 发表日期: 2024-10-04
• 页码: 99-105
• 关键词: aromatic metamorphosis; photoredox catalysis; thiophene; insight; indole; bonds; acids

摘要

The identity of a heteroatom within an aromatic ring influences the chemical properties of that heterocyclic compound. Systematically evaluating the effect of a single atom, however, poses synthetic challenges, primarily as a result of thermodynamic mismatches in atomic exchange processes. We present a photocatalytic strategy that swaps an oxygen atom of furan with a nitrogen group, directly converting the furan into a pyrrole analog in a single intermolecular reaction. High compatibility was observed with various furan derivatives and nitrogen nucleophiles commonly used in drug discovery, and the late-stage functionalization furnished otherwise difficult-to-access pyrroles from naturally occurring furans of high molecular complexity. Mechanistic analysis suggested that polarity inversion through single electron transfer initiates the redox-neutral atom exchange processes at room temperature.