“On Water” Cationic Ruthenium(II) Catalysed Direct Aryl C(sp2)−H Amidation of Biorelevant Heterocyclic Scaffolds

IF 3.5 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY
Bhavin V. Pipaliya, Nirjhar Saha, Asit K. Chakraborti
{"title":"“On Water” Cationic Ruthenium(II) Catalysed Direct Aryl C(sp2)−H Amidation of Biorelevant Heterocyclic Scaffolds","authors":"Bhavin V. Pipaliya,&nbsp;Nirjhar Saha,&nbsp;Asit K. Chakraborti","doi":"10.1002/asia.202401505","DOIUrl":null,"url":null,"abstract":"<p>Ru(II)-Catalyzed “On Water” direct aryl C(sp<sup>2</sup>)−H amidation of 2-arylbenzo[<i>d</i>]-thiazole/oxazole with acyl azide is reported under silver-free condition. Deuterium scrambling experiments suggested reversible C−H activation catalyzed by active cationic ruthenium species. The organic solvents such as DCE, DMF, DMSO, MeCN, dioxane, and PhMe were not conducive for the C−H amidation except for PhCl in which case, however, inferior yield (31 %) was obtained. Water plays critical roles (i) during the formation of active cationic Ru-species, (ii) as proton scavenger during ligand-assisted C−H activation through hydrogen bond formation as evidenced by solvent kinetic isotope effect, and (iii) in the final protodissociation step. The mechanistic proposal resembles secondary coordination sphere hydrogen bond controlled transition metal catalysis showcasing the aryl C−H amidation through outer sphere nitrene insertion. The “on water” aryl C−H amidation protocol showed wide substrate scope with respect to the 2-arylbenzo[<i>d</i>]-thiazole/oxazole scaffold as well as the aryl moiety of the aroyl azide. While the applicability of the Ru(II)-catalysed “on water” C−H amidation protocol to 2-arylbenzo[<i>d</i>]-thiazole and 2-arylbenzo[<i>d</i>]-oxazole demonstrates its scope with respect to the directing group the effectiveness for sulfonamidation and phosphoramidation further broaden the synthetic scope.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":"20 6","pages":""},"PeriodicalIF":3.5000,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemistry - An Asian Journal","FirstCategoryId":"1","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/asia.202401505","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0

Abstract

Ru(II)-Catalyzed “On Water” direct aryl C(sp2)−H amidation of 2-arylbenzo[d]-thiazole/oxazole with acyl azide is reported under silver-free condition. Deuterium scrambling experiments suggested reversible C−H activation catalyzed by active cationic ruthenium species. The organic solvents such as DCE, DMF, DMSO, MeCN, dioxane, and PhMe were not conducive for the C−H amidation except for PhCl in which case, however, inferior yield (31 %) was obtained. Water plays critical roles (i) during the formation of active cationic Ru-species, (ii) as proton scavenger during ligand-assisted C−H activation through hydrogen bond formation as evidenced by solvent kinetic isotope effect, and (iii) in the final protodissociation step. The mechanistic proposal resembles secondary coordination sphere hydrogen bond controlled transition metal catalysis showcasing the aryl C−H amidation through outer sphere nitrene insertion. The “on water” aryl C−H amidation protocol showed wide substrate scope with respect to the 2-arylbenzo[d]-thiazole/oxazole scaffold as well as the aryl moiety of the aroyl azide. While the applicability of the Ru(II)-catalysed “on water” C−H amidation protocol to 2-arylbenzo[d]-thiazole and 2-arylbenzo[d]-oxazole demonstrates its scope with respect to the directing group the effectiveness for sulfonamidation and phosphoramidation further broaden the synthetic scope.

“On Water”阳离子钌(II)催化生物相关杂环支架直接芳基C(sp2)-H酰胺化。
报道了Ru(II)在无银条件下催化2-芳基苯并[d]-噻唑/恶唑与酰基叠氮化物的“On Water”直接芳基C(sp2)-H酰胺化反应。氘置乱实验表明,活性阳离子钌可催化可逆碳氢活化。除PhCl外,DCE、DMF、DMSO、MeCN、二恶烷、PhMe等有机溶剂均不利于C-H酰胺化,但其收率较低(31%)。水在以下几个方面发挥着至关重要的作用:(1)在活性阳离子钌的形成过程中;(2)在溶剂动力学同位素效应证明的配体辅助C-H通过氢键形成活化过程中作为质子清除剂;(3)在最后的原解离步骤中。机理建议类似于二级配位球氢键控制的过渡金属催化,通过外球插入亚硝基实现芳基C-H酰胺化。对2-芳基苯并[d]-噻唑/恶唑支架以及芳基叠氮化物的芳基部分,“on - water”芳基C-H酰胺化方案显示出广泛的底物范围。Ru(II)催化的“on - water”C-H酰胺化方案对2-芳基苯并[d]-噻唑和2-芳基苯并[d]-恶唑的适用性表明了其在导向基团上的适用范围,而磺化和磷酸化的有效性进一步拓宽了合成范围。
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
Chemistry - An Asian Journal
Chemistry - An Asian Journal 化学-化学综合
CiteScore
7.00
自引率
2.40%
发文量
535
审稿时长
1.3 months
期刊介绍: Chemistry—An Asian Journal is an international high-impact journal for chemistry in its broadest sense. The journal covers all aspects of chemistry from biochemistry through organic and inorganic chemistry to physical chemistry, including interdisciplinary topics. Chemistry—An Asian Journal publishes Full Papers, Communications, and Focus Reviews. A professional editorial team headed by Dr. Theresa Kueckmann and an Editorial Board (headed by Professor Susumu Kitagawa) ensure the highest quality of the peer-review process, the contents and the production of the journal. Chemistry—An Asian Journal is published on behalf of the Asian Chemical Editorial Society (ACES), an association of numerous Asian chemical societies, and supported by the Gesellschaft Deutscher Chemiker (GDCh, German Chemical Society), ChemPubSoc Europe, and the Federation of Asian Chemical Societies (FACS).
×
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