Tuning band structures of Hf-PCN-224(M) for β-Carbonyl C(sp3)-H bond activation and difunctionalization: Tandem C(sp3) radical cross-coupling through photoredox

IF 20.2 1区化学 Q1 CHEMISTRY, PHYSICAL

Applied Catalysis B: Environmental Pub Date : 2023-02-01 DOI:10.1016/j.apcatb.2022.122049

Lingjuan Zhang , Lijuan Ma , Jincong Yuan , Xian-Ming Zhang , Zhiyong Tang

{"title":"Tuning band structures of Hf-PCN-224(M) for β-Carbonyl C(sp3)-H bond activation and difunctionalization: Tandem C(sp3) radical cross-coupling through photoredox","authors":"Lingjuan Zhang , Lijuan Ma , Jincong Yuan , Xian-Ming Zhang , Zhiyong Tang","doi":"10.1016/j.apcatb.2022.122049","DOIUrl":null,"url":null,"abstract":"<div>The construction of C(sp3)-C(sp3) bonds by different C(sp3) radicals coupling reactions is still unexplored due to the high bond dissociation energy of C(sp3)-H bond and the difficulty for selective generating of C(sp3) radical. Benefiting from the precisely regulating for band structures of Hf-PCN-224(M), the β-carbonyl C(sp3)-H bonds are effectively oxidized by photo-generated holes to affording C(sp3) radicals in this work. C(sp3)-C(sp3) and C(sp3)-O bonds are constructed by tandem radical-radical cross-coupling, hydrogen atom transfer (HAT), and radical-radical cross-coupling between two C(sp3)-H bonds, enabling an effective C3-difunctionalization of indolin-2-ones under photo-thermo synergetic catalysis on Hf-PCN-224(Cu). Significantly, OH serves as triple roles: introduced hydroxyl group in situ, HAT abstractor and α-heteroatom for secondary activating C(sp3)-H bonds. Control experiments, EPR spectroscopy and DFT calculation provide insight into the tandem radicals cross-coupling mechanism. This operable strategy opens up a door for the difunctionalization of C(sp3)-H bonds in heterogeneous photoredox manner.</div>","PeriodicalId":244,"journal":{"name":"Applied Catalysis B: Environmental","volume":"321 ","pages":"Article 122049"},"PeriodicalIF":20.2000,"publicationDate":"2023-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Applied Catalysis B: Environmental","FirstCategoryId":"1","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0926337322009900","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

The construction of C(sp³)-C(sp³) bonds by different C(sp³) radicals coupling reactions is still unexplored due to the high bond dissociation energy of C(sp³)-H bond and the difficulty for selective generating of C(sp³) radical. Benefiting from the precisely regulating for band structures of Hf-PCN-224(M), the β-carbonyl C(sp³)-H bonds are effectively oxidized by photo-generated holes to affording C(sp³) radicals in this work. C(sp³)-C(sp³) and C(sp³)-O bonds are constructed by tandem radical-radical cross-coupling, hydrogen atom transfer (HAT), and radical-radical cross-coupling between two C(sp³)-H bonds, enabling an effective C₃-difunctionalization of indolin-2-ones under photo-thermo synergetic catalysis on Hf-PCN-224(Cu). Significantly, OH serves as triple roles: introduced hydroxyl group in situ, HAT abstractor and α-heteroatom for secondary activating C(sp³)-H bonds. Control experiments, EPR spectroscopy and DFT calculation provide insight into the tandem radicals cross-coupling mechanism. This operable strategy opens up a door for the difunctionalization of C(sp³)-H bonds in heterogeneous photoredox manner.

查看原文本刊更多论文

调节Hf-PCN-224(M)对β-羰基C(sp3)-氢键激活和双官能化的带结构:通过光氧化还原串联C(sp3)自由基交叉偶联

由于C(sp3)-H键的键解离能较高，且C(sp3)自由基难以选择性生成，不同的C(sp3)自由基偶联反应对C(sp3)-C(sp3)键的构建仍未被探索。得益于对Hf-PCN-224(M)的带结构的精确调控，本研究中β-羰基C(sp3)-H键被光生空穴有效氧化生成C(sp3)自由基。C(sp3)-C(sp3)和C(sp3)-O键通过两个C(sp3)-H键之间的串联自由基-自由基交叉偶联、氢原子转移(HAT)和自由基-自由基交叉偶联构建，在Hf-PCN-224(Cu)的光热协同催化下，吲哚啉-2- 1实现了有效的c3双官能化。值得注意的是，OH具有三重作用:原位引入羟基、HAT萃取剂和α-杂原子，二级激活C(sp3)-H键。控制实验，EPR光谱和DFT计算提供了对串联自由基交叉耦合机理的深入了解。这种可操作的策略为C(sp3)-H键在非均相光氧化还原方式下的双官能化打开了一扇门。

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

Applied Catalysis B: Environmental 环境科学-工程：化工

CiteScore

38.60

自引率

6.30%

发文量

1117

审稿时长

24 days

期刊介绍： Applied Catalysis B: Environment and Energy (formerly Applied Catalysis B: Environmental) is a journal that focuses on the transition towards cleaner and more sustainable energy sources. The journal's publications cover a wide range of topics, including: 1.Catalytic elimination of environmental pollutants such as nitrogen oxides, carbon monoxide, sulfur compounds, chlorinated and other organic compounds, and soot emitted from stationary or mobile sources. 2.Basic understanding of catalysts used in environmental pollution abatement, particularly in industrial processes. 3.All aspects of preparation, characterization, activation, deactivation, and regeneration of novel and commercially applicable environmental catalysts. 4.New catalytic routes and processes for the production of clean energy, such as hydrogen generation via catalytic fuel processing, and new catalysts and electrocatalysts for fuel cells. 5.Catalytic reactions that convert wastes into useful products. 6.Clean manufacturing techniques that replace toxic chemicals with environmentally friendly catalysts. 7.Scientific aspects of photocatalytic processes and a basic understanding of photocatalysts as applied to environmental problems. 8.New catalytic combustion technologies and catalysts. 9.New catalytic non-enzymatic transformations of biomass components. The journal is abstracted and indexed in API Abstracts, Research Alert, Chemical Abstracts, Web of Science, Theoretical Chemical Engineering Abstracts, Engineering, Technology & Applied Sciences, and others.