Benzylic C(sp3)−H Azidation: Copper vs Iron Catalysis

IF 1.5 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY
Angel Rentería-Gómez, Rubén O. Torres-Ochoa, Pierre Palamini, Raphaël Simonet-Davin, Qian Wang, Jérôme Waser, Jieping Zhu
{"title":"Benzylic C(sp3)−H Azidation: Copper vs Iron Catalysis","authors":"Angel Rentería-Gómez,&nbsp;Rubén O. Torres-Ochoa,&nbsp;Pierre Palamini,&nbsp;Raphaël Simonet-Davin,&nbsp;Qian Wang,&nbsp;Jérôme Waser,&nbsp;Jieping Zhu","doi":"10.1002/hlca.202400004","DOIUrl":null,"url":null,"abstract":"<p>The generation of benzylic radicals through hydrogen atom abstraction (HAT) has been a recent research focus and various C(sp<sup>3</sup>)−H bond functionalization protocols have been developed relying on this elementary step. We report herein copper- and iron-catalyzed C(sp<sup>3</sup>)−H benzylic azidation reactions using <i>m</i>CPBA and NFSI as oxidant, respectively, and TMSN<sub>3</sub> as azide source. The reaction is thought to be initiated <i>via</i> intermolecular abstraction of benzylic hydrogen by the <i>in situ</i> generated heteroatom-centered radicals. The Fe(OTf)<sub>3</sub>-catalyzed azidation protocol displays good chemoselectivity as it takes place preferentially at the secondary and tertiary benzylic C(sp<sup>3</sup>)−H bonds over the primary benzylic and tertiary aliphatic carbons. Efforts on the development of catalytic enantioselective processes are also documented.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":1.5000,"publicationDate":"2024-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202400004","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Helvetica Chimica Acta","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/hlca.202400004","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0

Abstract

The generation of benzylic radicals through hydrogen atom abstraction (HAT) has been a recent research focus and various C(sp3)−H bond functionalization protocols have been developed relying on this elementary step. We report herein copper- and iron-catalyzed C(sp3)−H benzylic azidation reactions using mCPBA and NFSI as oxidant, respectively, and TMSN3 as azide source. The reaction is thought to be initiated via intermolecular abstraction of benzylic hydrogen by the in situ generated heteroatom-centered radicals. The Fe(OTf)3-catalyzed azidation protocol displays good chemoselectivity as it takes place preferentially at the secondary and tertiary benzylic C(sp3)−H bonds over the primary benzylic and tertiary aliphatic carbons. Efforts on the development of catalytic enantioselective processes are also documented.

Abstract Image

Abstract Image

苄基 C(sp3)-H 氮化:铜催化与铁催化
通过氢原子抽取(HAT)生成苄基自由基是近年来的研究重点,各种 C(sp3)-H 键官能化方案都是基于这一基本步骤开发的。我们在此报告铜催化和铁催化的 C(sp3)-H 苄基叠氮反应,分别使用 mCPBA 和 NFSI 作为氧化剂,TMSN3 作为叠氮源。该反应被认为是通过原位生成的以杂原子为中心的自由基在分子间抽取苄基氢而引发的。Fe(OTf)3 催化的叠氮化反应具有良好的化学选择性,因为它优先发生在二级和三级苄基 C(sp3)-H 键上,而不是一级苄基和三级脂肪族碳上。此外,还记录了开发催化对映体选择性工艺的努力。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
求助全文
约1分钟内获得全文 求助全文
来源期刊
Helvetica Chimica Acta
Helvetica Chimica Acta 化学-化学综合
CiteScore
3.00
自引率
0.00%
发文量
60
审稿时长
2.3 months
期刊介绍: Helvetica Chimica Acta, founded by the Swiss Chemical Society in 1917, is a monthly multidisciplinary journal dedicated to the dissemination of knowledge in all disciplines of chemistry (organic, inorganic, physical, technical, theoretical and analytical chemistry) as well as research at the interface with other sciences, where molecular aspects are key to the findings. Helvetica Chimica Acta is committed to the publication of original, high quality papers at the frontier of scientific research. All contributions will be peer reviewed with the highest possible standards and published within 3 months of receipt, with no restriction on the length of the papers and in full color.
×
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:481959085
Book学术官方微信