Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

You’ve supercharged your research process with ACS and Mendeley!

STEP 1:
Click to create an ACS ID

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

MENDELEY PAIRING EXPIRED
Your Mendeley pairing has expired. Please reconnect
ACS Publications. Most Trusted. Most Cited. Most Read
Switchable Radical Carbonylation by Philicity Regulation

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Am. Chem. Soc. 2022, 144, 32, 14923-14935
    Article

    Switchable Radical Carbonylation by Philicity Regulation
    Click to copy article linkArticle link copied!

    • Bin Lu
      Bin Lu
      Key Laboratory of Pesticides & Chemical Biology Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P. R. China
      More by Bin Lu
    • Minghao Xu
      Minghao Xu
      Materials, Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, P. R. China
      More by Minghao Xu
    • Xiaotian Qi
      Xiaotian Qi
      Materials, Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, P. R. China
      More by Xiaotian Qi
      Orcidhttps://orcid.org/0000-0001-5420-5958
    • Min Jiang
      Min Jiang
      College of Materials, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou 310036, P. R. China
      More by Min Jiang
    • Wen-Jing Xiao*
      Wen-Jing Xiao
      Key Laboratory of Pesticides & Chemical Biology Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P. R. China
      State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, P. R. China
      *Email: [email protected]
      More by Wen-Jing Xiao
      Orcidhttps://orcid.org/0000-0002-9318-6021
    • Jia-Rong Chen*
      Jia-Rong Chen
      Key Laboratory of Pesticides & Chemical Biology Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P. R. China
      School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, P. R. China
      *Email: [email protected]
      More by Jia-Rong Chen
      Orcidhttps://orcid.org/0000-0001-6054-2547
    Other Access OptionsSupporting Information (1)

    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2022, 144, 32, 14923–14935
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.2c06677
    Published August 8, 2022
    Copyright © 2022 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    Carbonylation reactions involving CO as readily available C1 synthons have become one of the most important tools for the construction of carbonyl compounds from feedstock chemicals. Despite numerous catalytic methods for carbonylation reactions proceeding via ionic or radical pathways, an inherent limitation to these methods is the need to control switchable single and double carbonylative formation of value-added products from the same and simple starting materials. Here, we describe a new strategy that exploits photoredox catalysis to regulate the philicity of amine coupling partners to drive switchable radical carbonylation reactions. In double carbonylation, amines were first transformed into nitrogen radical cations by single-electron transfer-oxidation and coupled with CO to form carbamoyl radicals, which further underwent radical cross-coupling with the incipient cyanoalkyl acyl radicals to afford the double carbonylation products. Upon the addition of stoichiometric 4-dimethylaminopyridine (DMAP), DMAP competitively traps the initially formed cyanoalkyl acyl radical to form the relatively stabilized cyanoalkyl acyl-DMAP salts that engaged in the subsequent substitution with the nucleophilic amines to produce the single carbonylation products. The reaction proceeded smoothly with excellent selectivity in the presence of various amine nucleophiles at room temperature, generating valuable amides and α-ketoamides in a versatile and controlled fashion. Combined experimental and computational studies provided mechanistic insights into the possible pathways.

    Copyright © 2022 American Chemical Society

    Subjects

    what are subjects

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    Supporting Information

    Click to copy section linkSection link copied!

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.2c06677.

    • Experimental procedures and characterization data for all the products (PDF)

    Terms & Conditions

    Electronic Supporting Information files are available without a subscription to ACS Web Editions. The American Chemical Society holds a copyright ownership interest in any copyrightable Supporting Information. Files available from the ACS website may be downloaded for personal use only. Users are not otherwise permitted to reproduce, republish, redistribute, or sell any Supporting Information from the ACS website, either in whole or in part, in either machine-readable form or any other form without permission from the American Chemical Society. For permission to reproduce, republish and redistribute this material, requesters must process their own requests via the RightsLink permission system. Information about how to use the RightsLink permission system can be found at http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!

    This article is cited by 18 publications.

    1. Zhi-Peng Ye, Meng Guo, Yong-Qing Ye, Chu-Ping Yuan, Hai-Long Wang, Jing-Song Yang, Hong-Bin Chen, Hao-Yue Xiang, Kai Chen, Hua Yang. Iodine(III)-Mediated Trifluoroacetylation of a C(sp2)–H or C(sp)–H Bond with Masked Trifluoroacyl Reagents. Organic Letters 2024, 26 (24) , 5196-5201. https://doi.org/10.1021/acs.orglett.4c01780
    2. Ming Li, Shanmei Xu, Dong-Ping Chen, Fan Gao, Shun-Xi Li, Shuang-Xi Zhu, Yi-Feng Qiu, Zheng-Jun Quan, Xi-Cun Wang, Yong-Min Liang. Palladium-Catalyzed Three-Component Cascade Carbonylation Reaction to Construct Benzofuran Derivatives. The Journal of Organic Chemistry 2024, 89 (11) , 7741-7746. https://doi.org/10.1021/acs.joc.4c00420
    3. Yaqi Deng, Zongjing Hu, Jian Xue, Jiabin Yin, Tong Zhu, Shunying Liu. Visible-Light-Promoted α-C(sp3)–H Amination of Ethers with Azoles and Amides. Organic Letters 2024, 26 (4) , 933-938. https://doi.org/10.1021/acs.orglett.3c04291
    4. Sangil Han, Kyra L. Samony, Rifat N. Nabi, Campbell A. Bache, Daniel K. Kim. Hydrotrifluoroacetylation of Alkenes via Designer Masked Acyl Reagents. Journal of the American Chemical Society 2023, 145 (21) , 11530-11536. https://doi.org/10.1021/jacs.3c04294
    5. Ming Li, Shun-Xi Li, Dong-ping Chen, Fan Gao, Yi-Feng Qiu, Xi-Cun Wang, Zheng-Jun Quan, Yong-Min Liang. Regioselective C–H Active Carbonylation via 1,4-Palladium Migration. Organic Letters 2023, 25 (16) , 2761-2766. https://doi.org/10.1021/acs.orglett.3c00567
    6. Hunter S. Sims, Mingji Dai. Palladium-Catalyzed Carbonylations: Application in Complex Natural Product Total Synthesis and Recent Developments. The Journal of Organic Chemistry 2023, 88 (8) , 4925-4941. https://doi.org/10.1021/acs.joc.2c02746
    7. Wuxin Zhou, Yang Long, Haifeng Xiang, Buyi Xu, Xiangge Zhou. Iron-Catalyzed C–C Bond Cleavage of Oximes for Direct Coupling of Benzothiazole in Water. The Journal of Organic Chemistry 2023, 88 (7) , 4875-4879. https://doi.org/10.1021/acs.joc.3c00197
    8. Jinglan Lei, Min Li, Qingqing Zhang, Shuyang Liu, Haifang Li, Lei Shi, Wen-Feng Jiang, Chunying Duan, Yunhe Jin. Visible-Light-Induced Radical Cascade Cross-Coupling via C(sp3)–H Activation and C–N/N–O Cleavage: Feasible Access to Methylenebisamide Derivatives. Organic Letters 2023, 25 (13) , 2300-2305. https://doi.org/10.1021/acs.orglett.3c00646
    9. Ming Li, Fan Gao, Dong-Yu Miao, Dong-ping Chen, Shun-Xi Li, Yi-Feng Qiu, Zheng-Jun Quan, Xi-Cun Wang, Yong-Min Liang. Redox Neutral Radical-Relay Nickel-Catalyzed Remote Carbonylation. Organic Letters 2023, 25 (13) , 2306-2311. https://doi.org/10.1021/acs.orglett.3c00654
    10. Xiao-Yu Lu, Jun-Chao Wang, Xiao-Mei Sun, Meng-Ting Gao, Weng-Jing Ying, Meng-Yuan Ge, Zheng-Huan Wei, Zi Liu, Xing-Ke Chen. Photoredox/Nickel Dual-Catalyzed Stereoselective Synthesis of Distal Cyano-Substituted Enamides. The Journal of Organic Chemistry 2023, 88 (1) , 513-524. https://doi.org/10.1021/acs.joc.2c02497
    11. Peng-Zi Wang, Yu-Jie Liang, Xue Wu, Wei Guan, Wen-Jing Xiao, Jia-Rong Chen. Copper-Catalyzed Three-Component Photo-ATRA-Type Reaction for Asymmetric Intermolecular C–O Coupling. ACS Catalysis 2022, 12 (17) , 10925-10937. https://doi.org/10.1021/acscatal.2c03576
    12. Han-Jun Ai, Fengqian Zhao, Xiao-Feng Wu. SET or TET? Iron-catalyzed aminocarbonylation of unactivated alkyl halides with amines, amides, and indoles via a substrate dependent mechanism. Chinese Journal of Catalysis 2023, 47 , 121-128. https://doi.org/10.1016/S1872-2067(22)64208-6
    13. Qihong Lai, Shanyi Chen, Linnan Zou, Chengzhi Lin, Shuling Huang, Lailing Fu, Lina Cai, Shunyou Cai. Syntheses of functionalized benzocoumarins by photoredox catalysis. Organic & Biomolecular Chemistry 2023, 21 (6) , 1181-1186. https://doi.org/10.1039/D2OB02225G
    14. Fuqing Zhang, Zixiang Wei, Wei Wu, Na Liu, Xinhan Li, Luqian Zou, Kaiming Wang, Jianbin Xu, Baomin Fan. Photocatalyst-free visible light driven synthesis of gem -dihaloenones from alkynes, tetrahalomethanes and water. Organic & Biomolecular Chemistry 2023, 21 (4) , 719-723. https://doi.org/10.1039/D2OB01983C
    15. Biquan Xiong, Chonghao Shi, Weifeng Xu, Yu Liu, Longzhi Zhu, Ke‐Wen Tang, Shuang‐Feng Yin, Wai‐Yeung Wong. Visible‐Light‐Induced Cascade Phosphinoylation/Cyclization of Phenacylmalononitriles with Secondary H ‐phosphine Oxides. Advanced Synthesis & Catalysis 2022, 364 (24) , 4392-4401. https://doi.org/10.1002/adsc.202201055
    16. Lin Zhu, Dian Song, Yi-Han Liu, Meng-Di Chen, Xin-Ru Zhang, Meng-Yan You, Jun-Long Zhan. Iron-catalyzed regioselective synthesis of ( E )-vinyl sulfones mediated by unprotected hydroxylamines. Organic & Biomolecular Chemistry 2022, 20 (46) , 9127-9131. https://doi.org/10.1039/D2OB01922A
    17. Fuyang Yue, Henan Ma, Hongjian Song, Yuxiu Liu, Jianyang Dong, Qingmin Wang. Alkylboronic acids as alkylating agents: photoredox-catalyzed alkylation reactions assisted by K 3 PO 4. Chemical Science 2022, 13 (45) , 13466-13474. https://doi.org/10.1039/D2SC05521J
    18. Youcan Zhang, Xiao-Feng Wu. Switchable Radical Carbonylation by Philicity Regulation. Chinese Journal of Organic Chemistry 2022, 42 (9) , 3007. https://doi.org/10.6023/cjoc202200050
    Download PDF
    Go to Journal of the American Chemical Society
    Get e-Alerts
    Get e-Alerts

    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2022, 144, 32, 14923–14935
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.2c06677
    Published August 8, 2022
    Copyright © 2022 American Chemical Society
    Request reuse permissions

    Article Views

    9874

    Altmetric

    -

    Citations

    18
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.