Visible Light Promotes PIII/PV‑Catalyzed Reductive N‑Arylation of Nitroarenes at Room Temperature

IF 13.1 1区 化学 Q1 CHEMISTRY, PHYSICAL
Bora Kang, Marissa N. Lavagnino, Jesse B. Gordon, Kristopher G. Reynolds, Daniel G. Nocera, Alexander T. Radosevich
{"title":"Visible Light Promotes PIII/PV‑Catalyzed Reductive N‑Arylation of Nitroarenes at Room Temperature","authors":"Bora Kang, Marissa N. Lavagnino, Jesse B. Gordon, Kristopher G. Reynolds, Daniel G. Nocera, Alexander T. Radosevich","doi":"10.1021/acscatal.5c04341","DOIUrl":null,"url":null,"abstract":"Visible-light irradiation is found to accelerate the reductive coupling of nitroarenes and arylboronic acids under the conditions of P<sup>III</sup>/P<sup>V</sup> catalysis. Specifically, blue-light (λ<sub>exc</sub> = 427 nm) illumination of a catalytic mixture composed of a redox active main group catalyst (1,2,2,3,4,4-hexamethylphosphetane <italic toggle=\"yes\">P</italic>-oxide, i.e., <bold>P</bold>·[O]) and terminal reductant (1,3-diphenyldisiloxane) enables formation of diarylamines from nitroarenes and arylboronic acids at ambient temperature. In situ <sup>31</sup>P NMR data demonstrate the importance of fast in situ P<sup>V</sup>O → P<sup>III</sup> reduction by the hydrosilane reductant to permit productive room temperature reductive coupling. Moreover, the present photochemical method expands the scope of the organophosphorus-catalyzed reductive coupling reaction to accommodate 2,6-disubstituted nitroarenes, which were previously poorly reactive under prior thermal (dark) reaction conditions. Transient absorption experiments are consistent with excitation of the nitroarene to generate a triplet excited state, which is quenched by intermolecular electron transfer from the P<sup>III</sup> resting state of the catalyst with rate constants near the diffusion-controlled limit (<italic toggle=\"yes\">k</italic> <sub>q</sub> = 2.93 × 10<sup>9</sup> M<sup>–1</sup> s<sup>–1</sup>). These results establish the successful interface of a P<sup>III</sup>/P<sup>V</sup> catalytic cycle with photon input, suggesting additional opportunities for photodriven methods that exploit organophosphorus-based catalytic intermediates.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"96 1","pages":""},"PeriodicalIF":13.1000,"publicationDate":"2025-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Catalysis ","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acscatal.5c04341","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0

Abstract

Visible-light irradiation is found to accelerate the reductive coupling of nitroarenes and arylboronic acids under the conditions of PIII/PV catalysis. Specifically, blue-light (λexc = 427 nm) illumination of a catalytic mixture composed of a redox active main group catalyst (1,2,2,3,4,4-hexamethylphosphetane P-oxide, i.e., P·[O]) and terminal reductant (1,3-diphenyldisiloxane) enables formation of diarylamines from nitroarenes and arylboronic acids at ambient temperature. In situ 31P NMR data demonstrate the importance of fast in situ PVO → PIII reduction by the hydrosilane reductant to permit productive room temperature reductive coupling. Moreover, the present photochemical method expands the scope of the organophosphorus-catalyzed reductive coupling reaction to accommodate 2,6-disubstituted nitroarenes, which were previously poorly reactive under prior thermal (dark) reaction conditions. Transient absorption experiments are consistent with excitation of the nitroarene to generate a triplet excited state, which is quenched by intermolecular electron transfer from the PIII resting state of the catalyst with rate constants near the diffusion-controlled limit (k q = 2.93 × 109 M–1 s–1). These results establish the successful interface of a PIII/PV catalytic cycle with photon input, suggesting additional opportunities for photodriven methods that exploit organophosphorus-based catalytic intermediates.
可见光促进室温下PIII/PV催化硝基芳烃的还原N -芳基化
在PIII/PV催化条件下,发现可见光照射可加速硝基芳烃与芳基硼酸的还原偶联反应。具体来说,在蓝光(λexc = 427 nm)照射下,由氧化还原活性主基团催化剂(1,2,2,3,4,4-六甲基磷-氧化物,即P·[O])和末端还原剂(1,3-二苯基二硅氧烷)组成的催化混合物能够在室温下由硝基芳烃和芳基硼酸生成二芳胺。原位31P核磁共振数据证明了氢硅烷还原剂快速原位PVO→PIII还原的重要性,以允许生产室温还原偶联。此外,目前的光化学方法扩大了有机磷催化的还原偶联反应的范围,以适应2,6-二取代的硝基芳烃,这些硝基芳烃在先前的热(暗)反应条件下反应性很差。瞬态吸收实验与硝基芳烃激发产生三重态激发态相一致,该激发态由催化剂PIII静息态的分子间电子转移猝灭,速率常数接近扩散控制极限(k q = 2.93 × 109 M-1 s-1)。这些结果建立了PIII/PV催化循环与光子输入的成功界面,为利用基于有机磷的催化中间体的光驱动方法提供了更多的机会。
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
ACS Catalysis
ACS Catalysis CHEMISTRY, PHYSICAL-
CiteScore
20.80
自引率
6.20%
发文量
1253
审稿时长
1.5 months
期刊介绍: ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.
×
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