A Photocatalytic Approach to Radical 1-(Trifluoromethyl)cyclopropanation

被引：0
作者：
Timmann, Sven [1 ]
Dilchert, Moritz T. H. [1 ]
Dietzel, Jorg [1 ]
Poeltl, Verena S. [1 ]
Wennekamp, Marc R. [1 ]
Golz, Christopher [1 ]
Alcarazo, Manuel [1 ]
机构：
[1] Georg August Univ Gottingen, Inst Organ & Biomol Chem, D-37077 Gottingen, Germany
来源：
ACS CATALYSIS | 2025年 / 15卷 / 09期
基金：
欧盟地平线“2020”; 欧洲研究理事会;
关键词：
bioisosteric replacement; photoredox catalysis; radical alkylation; sulfonium salts; 1-(trifluoromethyl)cyclopropane; DISCOVERY; FUNCTIONALIZATION; TRIFLUOROMETHYL; OPTIMIZATION; POTENT; SCOPE;
D O I：
10.1021/acscatal.5c01642
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
A simple protocol for the multigram-scale synthesis of 5-(1-(trifluoromethyl)cyclopropyl)dibenzothiophenium triflate is reported. This benchtop-stable reagent efficiently releases 1-(trifluoromethyl)cyclopropyl radicals under mild photochemical conditions, enabling the straightforward incorporation of that privileged chemotype at previously nonfunctionalized positions of (hetero)arenes and silyl enol ethers. The trifluoromethylcyclopropanation protocols herein reported are associated with an exceedingly broad substrate scope, remarkable functional group compatibility, high regioselectivity, and synthetically useful yields, making this reagent especially suitable for the preparation of medicinally relevant building blocks.
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收藏
页码：7232 / 7240
页数：9
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  • [1] CF3-Cyclobutanes: Synthesis, Properties, and Evaluation as a Unique tert-Butyl Group Analogue
    Ahunovych, Volodymyr
    Klipkov, Anton A.
    Bugera, Maksym
    Tarasenko, Karen
    Trofymchuk, Serhii
    Razhyk, Bohdan
    Boretskyi, Andrii
    Stanko, Oleh
    Panasiuk, Yaroslav
    Shablykin, Oleh
    Al-Maali, Galeb
    Lesyk, Dmytro
    Klymenko-Ulianov, Oleksii
    Horbatok, Kateryna
    Bodenchuk, Iryna
    Kosach, Viktoriia
    Borysko, Petro
    Kubyshkin, Vladimir
    Mykhailiuk, Pavel K.
    [J]. JACS AU, 2024, 4 (11): : 4507 - 4517
  • [2] General and Scalable Approach to Trifluoromethyl-Substituted Cyclopropanes
    Ahunovych, Volodymyr
    Klipkov, Anton A.
    Bugera, Maksym
    Tarasenko, Karen
    Trofymchuk, Serhii
    Stanko, Oleh
    Boretskyi, Andrii
    Zheludenko, Mykola
    Sadkova, Iryna V.
    Mykhailiuk, Pavel K.
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 2023, 88 (06) : 3859 - 3870
  • [3] Dibenzothiophenium Salts: Practical Alternatives to Hypervalent I(III)-Based Reagents
    Alcarazo, Manuel
    [J]. ACCOUNTS OF CHEMICAL RESEARCH, 2025, 58 (04) : 635 - 646
  • [4] The pentafluorosulfanyl group in cannabinoid receptor ligands: synthesis and comparison with trifluoromethyl and tert-butyl analogues
    Altomonte, Stefano
    Baillie, Gemma L.
    Ross, Ruth A.
    Riley, Jennifer
    Zanda, Matteo
    [J]. RSC ADVANCES, 2014, 4 (39): : 20164 - 20176
  • [5] Metabolically Stable tert-Butyl Replacement
    Barnes-Seeman, David
    Jain, Monish
    Bell, Leslie
    Ferreira, Suzie
    Cohen, Scott
    Chen, Xiao-Hui
    Amin, Jakal
    Snodgrass, Brad
    Hatsis, Panos
    [J]. ACS MEDICINAL CHEMISTRY LETTERS, 2013, 4 (06): : 514 - 516
  • [6] Discovery of a Potent, Selective T-type Calcium Channel Blocker as a Drug Candidate for the Treatment of Generalized Epilepsies
    Bezencon, Olivier
    Heidmann, Bibia
    Siegrist, Romain
    Stamm, Simon
    Richard, Sylvia
    Pozzi, Davide
    Corminboeuf, Olivier
    Roch, Catherine
    Kessler, Melanie
    Ertel, Eric A.
    Reymond, Isabelle
    Pfeifer, Thomas
    de Kanter, Ruben
    Toeroek-Schafroth, Michael
    Moccia, Luca G.
    Mawet, Jacques
    Moon, Richard
    Rey, Markus
    Capeleto, Bruno
    Fournier, Elvire
    [J]. JOURNAL OF MEDICINAL CHEMISTRY, 2017, 60 (23) : 9769 - 9789
  • [7] Recent Progress Toward the Synthesis of Trifluoromethyl- and Difluoromethyl-Substituted Cyclopropanes
    Bos, Maxence
    Poisson, Thomas
    Pannecoucke, Xavier
    Charette, Andre B.
    Jubault, Philippe
    [J]. CHEMISTRY-A EUROPEAN JOURNAL, 2017, 23 (21) : 4950 - 4961
  • [8] Mechanistic Studies in Photocatalysis
    Buzzetti, Luca
    Crisenza, Giacomo E. M.
    Melchiorre, Paolo
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2019, 58 (12) : 3730 - 3747
  • [9] Mild and Diazo-Free Synthesis of Trifluoromethyl-Cyclopropanes Using Sulfonium Ylides
    Cyr, Patrick
    Flynn-Robitaille, Joel
    Boissarie, Patrick
    Marinier, Anne
    [J]. ORGANIC LETTERS, 2019, 21 (07) : 2265 - 2268
  • [10] Electrophilicity and nucleophilicity index for radicals
    De Vleeschouwer, Freija
    Van Speybroeck, Veronique
    Waroquier, Michel
    Geerlings, Paul
    De Proft, Frank
    [J]. ORGANIC LETTERS, 2007, 9 (14) : 2721 - 2724
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