流动中氢原子转移光催化制备五元杂环和碳环的缩合策略。

IF 6.6 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
ChemSusChem Pub Date : 2025-06-20 DOI:10.1002/cssc.202501012
Filippo Sacchelli, Elena Quadri, Luna Raineri, Alexandra Jorea, Marzia Pessina, Anna Lo Presti, Nicola Della Ca', Davide Ravelli, Luca Capaldo
{"title":"流动中氢原子转移光催化制备五元杂环和碳环的缩合策略。","authors":"Filippo Sacchelli, Elena Quadri, Luna Raineri, Alexandra Jorea, Marzia Pessina, Anna Lo Presti, Nicola Della Ca', Davide Ravelli, Luca Capaldo","doi":"10.1002/cssc.202501012","DOIUrl":null,"url":null,"abstract":"<p><p>Five-membered heterocycles such as pyrroles and thiophenes, along with cyclopentenones, are key scaffolds in pharmaceutical chemistry. However, the synthesis of these motifs via diversity oriented synthesis is hindered by the limited accessibility of unsymmetrical 1,4-diketones. Herein, a practical and sustainable flow protocol is presented for the telescoped synthesis of pyrroles, thiophenes, and cyclopentenones. The process begins with decatungstate-photocatalyzed hydrogen atom transfer from aldehydes to generate acyl radicals, which undergo regioselective addition to functionalized enones. The resulting diketones are then fed into a second reactor-tubular or packed-bed-to undergo Paal-Knorr or Hunsdiecker condensation reactions. This modular strategy enables rapid access to densely substituted, biorelevant hetero- and carbocycles with unconventional substitution patterns, as demonstrated by the synthesis of tri-, tetra-, and pentasubstituted pyrroles and thiophenes, and mono-, di-, and trisubstituted cyclopentenones.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e2501012"},"PeriodicalIF":6.6000,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"A Telescoped Strategy for the Preparation of Five-Membered Hetero- and Carbocycles via Hydrogen Atom Transfer Photocatalysis in Flow.\",\"authors\":\"Filippo Sacchelli, Elena Quadri, Luna Raineri, Alexandra Jorea, Marzia Pessina, Anna Lo Presti, Nicola Della Ca', Davide Ravelli, Luca Capaldo\",\"doi\":\"10.1002/cssc.202501012\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>Five-membered heterocycles such as pyrroles and thiophenes, along with cyclopentenones, are key scaffolds in pharmaceutical chemistry. However, the synthesis of these motifs via diversity oriented synthesis is hindered by the limited accessibility of unsymmetrical 1,4-diketones. Herein, a practical and sustainable flow protocol is presented for the telescoped synthesis of pyrroles, thiophenes, and cyclopentenones. The process begins with decatungstate-photocatalyzed hydrogen atom transfer from aldehydes to generate acyl radicals, which undergo regioselective addition to functionalized enones. The resulting diketones are then fed into a second reactor-tubular or packed-bed-to undergo Paal-Knorr or Hunsdiecker condensation reactions. This modular strategy enables rapid access to densely substituted, biorelevant hetero- and carbocycles with unconventional substitution patterns, as demonstrated by the synthesis of tri-, tetra-, and pentasubstituted pyrroles and thiophenes, and mono-, di-, and trisubstituted cyclopentenones.</p>\",\"PeriodicalId\":149,\"journal\":{\"name\":\"ChemSusChem\",\"volume\":\" \",\"pages\":\"e2501012\"},\"PeriodicalIF\":6.6000,\"publicationDate\":\"2025-06-20\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ChemSusChem\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1002/cssc.202501012\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ChemSusChem","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/cssc.202501012","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0

摘要

吡咯和噻吩等五元杂环化合物与环戊烯酮是药物化学中的关键支架。然而,由于不对称的1,4-二酮的可及性有限,通过多样性定向合成(DOS)合成这些基序受到阻碍。我们报告了一个实用的和可持续的流程协议伸缩合成吡咯,噻吩和环戊酮。这个过程开始于十钨酸盐光催化的氢原子转移(HAT)从醛生成酰基自由基,酰基自由基经过区域选择性加成到功能化的烯酮上。然后将生成的二酮送入第二个反应器管状或填充床,进行Paal-Knorr或Hunsdiecker转化。这种模块化策略可以快速获得具有非常规取代模式的密集取代、生物相关的杂环和碳环,如三、四、五取代的吡咯和噻吩,以及单、二、三取代的环戊烯酮的合成。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
A Telescoped Strategy for the Preparation of Five-Membered Hetero- and Carbocycles via Hydrogen Atom Transfer Photocatalysis in Flow.

Five-membered heterocycles such as pyrroles and thiophenes, along with cyclopentenones, are key scaffolds in pharmaceutical chemistry. However, the synthesis of these motifs via diversity oriented synthesis is hindered by the limited accessibility of unsymmetrical 1,4-diketones. Herein, a practical and sustainable flow protocol is presented for the telescoped synthesis of pyrroles, thiophenes, and cyclopentenones. The process begins with decatungstate-photocatalyzed hydrogen atom transfer from aldehydes to generate acyl radicals, which undergo regioselective addition to functionalized enones. The resulting diketones are then fed into a second reactor-tubular or packed-bed-to undergo Paal-Knorr or Hunsdiecker condensation reactions. This modular strategy enables rapid access to densely substituted, biorelevant hetero- and carbocycles with unconventional substitution patterns, as demonstrated by the synthesis of tri-, tetra-, and pentasubstituted pyrroles and thiophenes, and mono-, di-, and trisubstituted cyclopentenones.

求助全文
通过发布文献求助,成功后即可免费获取论文全文。 去求助
来源期刊
ChemSusChem
ChemSusChem 化学-化学综合
CiteScore
15.80
自引率
4.80%
发文量
555
审稿时长
1.8 months
期刊介绍: ChemSusChem Impact Factor (2016): 7.226 Scope: Interdisciplinary journal Focuses on research at the interface of chemistry and sustainability Features the best research on sustainability and energy Areas Covered: Chemistry Materials Science Chemical Engineering Biotechnology
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术官方微信