Jinyu Tang, Xi Zhao, Jinxuan Ni, Yanping Huo, Yang Gao, Xianwei Li, Yan Liu, Keiji Maruoka and Qian Chen
{"title":"可见光诱导的烯丙基醚 C（sp3）-C（sp2）σ键有氧光氧化裂解作用","authors":"Jinyu Tang, Xi Zhao, Jinxuan Ni, Yanping Huo, Yang Gao, Xianwei Li, Yan Liu, Keiji Maruoka and Qian Chen","doi":"10.1039/D4QO01243G","DOIUrl":null,"url":null,"abstract":"<p >The development of the C–C bond cleavage of allylarenes is of vital importance. However, the cleavage of C(sp<small><sup>3</sup></small>)–C(sp<small><sup>2</sup></small>) σ-bonds has been rarely reported previously. Herein, we disclose an efficient and green photooxidative cleavage of C(sp<small><sup>3</sup></small>)–C(sp<small><sup>2</sup></small>) σ-bonds of allylarenes under the irradiation of blue LEDs using anthraquinone (AQ) as the photocatalyst and eco-friendly molecular oxygen (O<small><sub>2</sub></small>) as the sole oxidant. The newly developed reaction shows broad substrate scopes under metal- and additive-free conditions, providing practical and scalable access to aromatic aldehydes and ketones. Preliminary mechanistic studies suggest that a delocalized allylic radical generated <em>via</em> a hydrogen atom transfer (HAT) between photoexcited AQ (AQ*) and the allylic C(sp<small><sup>3</sup></small>)–H bond might be involved in this transformation.</p>","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":4.6000,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Visible light-induced aerobic photooxidative cleavage of C(sp3)–C(sp2) σ-bonds of allylarenes†\",\"authors\":\"Jinyu Tang, Xi Zhao, Jinxuan Ni, Yanping Huo, Yang Gao, Xianwei Li, Yan Liu, Keiji Maruoka and Qian Chen\",\"doi\":\"10.1039/D4QO01243G\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >The development of the C–C bond cleavage of allylarenes is of vital importance. However, the cleavage of C(sp<small><sup>3</sup></small>)–C(sp<small><sup>2</sup></small>) σ-bonds has been rarely reported previously. Herein, we disclose an efficient and green photooxidative cleavage of C(sp<small><sup>3</sup></small>)–C(sp<small><sup>2</sup></small>) σ-bonds of allylarenes under the irradiation of blue LEDs using anthraquinone (AQ) as the photocatalyst and eco-friendly molecular oxygen (O<small><sub>2</sub></small>) as the sole oxidant. The newly developed reaction shows broad substrate scopes under metal- and additive-free conditions, providing practical and scalable access to aromatic aldehydes and ketones. Preliminary mechanistic studies suggest that a delocalized allylic radical generated <em>via</em> a hydrogen atom transfer (HAT) between photoexcited AQ (AQ*) and the allylic C(sp<small><sup>3</sup></small>)–H bond might be involved in this transformation.</p>\",\"PeriodicalId\":97,\"journal\":{\"name\":\"Organic Chemistry Frontiers\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.6000,\"publicationDate\":\"2024-09-18\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organic Chemistry Frontiers\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2024/qo/d4qo01243g\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, ORGANIC\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic Chemistry Frontiers","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/qo/d4qo01243g","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
引用次数: 0
摘要
开发烯丙基酚的 C-C 键裂解技术至关重要。然而，C(sp3)-C(sp2) σ键的裂解此前鲜有报道。在此，我们以蒽醌（AQ）为光催化剂，以环保的分子氧（O2）为唯一氧化剂，揭示了在蓝光 LED 的照射下，高效、绿色地光氧化裂解烯丙基酚的 C（sp3）-C（sp2）σ键的方法。在无金属和添加剂的条件下，新开发的反应显示出广泛的底物范围，为芳香醛和酮提供了实用和可扩展的途径。初步的机理研究表明，通过光激发 AQ (AQ*) 与烯丙基 C(sp3)-H 键之间的氢原子转移 (HAT) 产生的脱局域烯丙基自由基可能参与了这一转化过程。
Visible light-induced aerobic photooxidative cleavage of C(sp3)–C(sp2) σ-bonds of allylarenes†
The development of the C–C bond cleavage of allylarenes is of vital importance. However, the cleavage of C(sp3)–C(sp2) σ-bonds has been rarely reported previously. Herein, we disclose an efficient and green photooxidative cleavage of C(sp3)–C(sp2) σ-bonds of allylarenes under the irradiation of blue LEDs using anthraquinone (AQ) as the photocatalyst and eco-friendly molecular oxygen (O2) as the sole oxidant. The newly developed reaction shows broad substrate scopes under metal- and additive-free conditions, providing practical and scalable access to aromatic aldehydes and ketones. Preliminary mechanistic studies suggest that a delocalized allylic radical generated via a hydrogen atom transfer (HAT) between photoexcited AQ (AQ*) and the allylic C(sp3)–H bond might be involved in this transformation.
期刊介绍：
Organic Chemistry Frontiers is an esteemed journal that publishes high-quality research across the field of organic chemistry. It places a significant emphasis on studies that contribute substantially to the field by introducing new or significantly improved protocols and methodologies. The journal covers a wide array of topics which include, but are not limited to, organic synthesis, the development of synthetic methodologies, catalysis, natural products, functional organic materials, supramolecular and macromolecular chemistry, as well as physical and computational organic chemistry.
京公网安备 11010802042870号
京ICP备2023020795号-1
分享
求助内容：
应助结果提醒方式：
扫码关注我们
