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Synlett 2024; 35(20): 2520-2524
DOI: 10.1055/a-2416-2329
letter
Special Issue to Celebrate the 75th Birthday of Prof. B. C. Ranu

C–H Activation: A Versatile Tool for the Synthesis of Niclosamide and Its Derivatives

Rachel Gundamalla
a   Fluoro-Agrochemicals, CSIR-Indian Institute of Chemical Technology, Hyderabad, 500 007, India
b   Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, 201002, India
,
Rajashaker Bantu
a   Fluoro-Agrochemicals, CSIR-Indian Institute of Chemical Technology, Hyderabad, 500 007, India
,
B. Sridhar
c   Laboratory of X-ray Crystallography, CSIR-Indian Institute of Chemical Technology, Hyderabad, 500 007, India
,
B. V. Subba Reddy∗
a   Fluoro-Agrochemicals, CSIR-Indian Institute of Chemical Technology, Hyderabad, 500 007, India
b   Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, 201002, India
› InstitutsangabenFinancial support was provided by CSIR, New Delhi.
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Abstract

A novel strategy has been developed for the direct and regioselective ortho-acetoxylation of N-(2-benzoylphenyl)benzamides through C–H activation using a catalytic amount of Pd(OAc)2 (5 mol%) and a stoichiometric amount of PhI(OAc)2 in a mixture of acetic anhydride and acetic acid. By using this protocol, a new series of niclosamide derivatives was produced in good yields. This is the first report on the synthesis of niclosamide and its derivatives by means of C–H functionalization. This newly developed method offers several advantages such as high regioselectivity, operational simplicity, and good to excellent yields. It provides a short three-step process for the synthesis of niclosamide involving acid–amine coupling, ortho-acetoxylation through C–H activation, and deacylation.

Key words

C–H bond activation - transition-metal catalysis - acetoxylation - niclosamide

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-2416-2329.
  • Supporting Information


Publikationsverlauf

Eingereicht: 25. Juli 2024

Angenommen nach Revision: 16. September 2024

Accepted Manuscript online:
16. September 2024

Artikel online veröffentlicht:
07. Oktober 2024

© 2024. Thieme. All rights reserved

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  • References and Notes

  • 1 Andrews P, Thyssen J, Lorke D. Pharmacol. Ther. 1983; 19: 245
    CrossrefPubMedSuche in Google Scholar
  • 2 Pearson RD, Hewlett EL. Ann. Intern. Med. 1985; 102: 550
    CrossrefPubMedSuche in Google Scholar
  • 3 WHO Expert Committee on the Selection and Use of Essential Medicines. The Selection and Use of Essential Medicines, Report of the WHO Expert Committee; Geneva: 2007. World Health Organization
    Suche in Google Scholar
  • 4 Weinbach EC, Garbus J. Nature 1969; 221: 1016
    CrossrefPubMedSuche in Google Scholar
  • 5 Williamson RL, Metcalf RL. Science 1967; 158: 1694
    CrossrefPubMedSuche in Google Scholar
  • 6 Frayha GJ, Smyth JD, Gobert JG, Savel J. Gen. Pharmacol. 1997; 28: 273
    CrossrefPubMedSuche in Google Scholar
  • 7 Swan GE. J. S. Afr. Vet. Assoc. 1999; 70: 61
    CrossrefPubMedSuche in Google Scholar
  • 8 Chen W, Mook RA. Jr, Premont RT, Wang J. Cell Signal. 2018; 41: 89
    CrossrefPubMedSuche in Google Scholar
  • 9 De Clercq E. Expert Rev. Anti-Infect. Ther. 2006; 4: 291
    CrossrefPubMedSuche in Google Scholar
  • 10 Wu C.-J, Jan J.-T, Chen C.-M, Hsieh H.-P, Hwang D.-R, Liu H.-W, Liu C.-Y, Huang H.-W, Chen S.-C, Lin R.-K, Chao Y.-S, Hsu JT. A. Antimicrob. Agents Chemother. 2004; 48: 2693
    CrossrefPubMedSuche in Google Scholar
  • 11 Xu J, Shi P.-Y, Li H, Zhou J. ACS Infect. Dis. 2020; 6: 909
    CrossrefPubMedSuche in Google Scholar
  • 12 Xu J, Berastegui-Cabrera J, Ye N, Carretero-Ledesma M, Pachón-Díaz J, Chen H, Pachón-Ibáñez ME, Sánchez-Céspedes J, Zhou J. J. Med. Chem. 2020; 63: 12830
    CrossrefPubMedSuche in Google Scholar
  • 13 Backer V, Sjöbring U, Sonne J, Weiss A, Hostrup M, Johansen HK, Becker V, Sonne DP, Balchen T, Jellingsø M, Sommer MO. A. Lancet Reg. Health Eur. 2021; 4: 100084
    CrossrefPubMedSuche in Google Scholar
  • 14 Jeon S, Meehyun K, Lee J, Choi I, Byun SY, Park S, Shum D, Kim S. Antimicrob. Agents Chemother. 2020; 64: e00819-20
    CrossrefPubMedSuche in Google Scholar
  • 15 Braga L, Ali H, Secco I, Chiavacci E, Neves G, Goldhill D, Penn R, Jimenez-Guardeño JM, Ortega-Prieto AM, Bussani R, Cannatà A, Rizzari G, Collesi C, Schneider E, Arosio D, Shah AM, Barclay WS, Malim MH, Burrone J, Giacca M. Nature 2021; 594: 88
    CrossrefPubMedSuche in Google Scholar
  • 16 Gassen NC, Papies J, Bajaj T, Emanuel J, Dethloff F, Chua RL, Trimpert J, Heinemann N, Niemeyer C, Weege F, Hönzke K, Aschman T, Heinz DE, Weckmann K, Ebert T, Zellner A, Lennarz M, Wyler E, Schroeder S, Richter A, Niemeyer D, Hoffmann K, Meyer TF, Heppner FL, Corman VM, Landthaler M, Hocke AC, Morkel M, Osterrieder N, Conrad C, Eils R, Radbruch H, Giavalisco P, Drosten C, Müller MA. Nat. Commun. 2021; 12: 3818
    CrossrefPubMedSuche in Google Scholar
  • 17 Blake S, Shaabani N, Eubanks LM, Maruyama J, Manning JT, Beutler N, Paessler S, Ji H, Teijaro JR, Janda KD. ACS Infect. Dis. 2021; 7: 2229
    CrossrefPubMedSuche in Google Scholar
  • 18 Shamim K, Xu M, Hu X, Lee EM, Lu X, Huang R, Shah P, Xu X, Chen CZ, Shen M, Guo H, Chen L, Itkin Z, Eastman RT, Shinn P, Klumpp-Thomas C, Michael S, Simeonov A, Lo DC, Ming G.-l, Song H, Tang H, Zheng W, Huang W. Bioorg. Med. Chem. Lett. 2021; 40: 127906
    CrossrefPubMedSuche in Google Scholar
  • 19 Li Y, Li PK, Roberts MJ, Arend RC, Samant RS, Buchsbaum DJ. Cancer Lett. 2014; 349: 8
    CrossrefPubMedSuche in Google Scholar
  • 20 Natarajan P, Renu C, Rani N, Sakshi Sakshi, Venugopalan P. Tetrahedron Lett. 2020; 61: 151529
    CrossrefSuche in Google Scholar
  • 25 CCDC 2373126 contains the supplementary crystallographic data for compound 2. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures
  • 27 4-Chloro-2-{[(2-chloro-4-nitrophenyl)amino]carbonyl}phenyl Acetate (2); Typical Procedure PhI(OAc)2 (1.14 g, 3.54 mmol) was added with stirring to 3-chloro-N-(2-chloro-4-nitrophenyl)benzamide (1; 1.0 g, 3.22 mmol) in 1:1 AcOH–Ac2O (10 mL), and the mixture was stirred for 5 min. Pd(OAc)2 (5 mol%, 36 mg) was then added at r.t., and the mixture was heated to 100 °C for 12 h until the reaction was complete (TLC). The resulting mixture was extracted with EtOAc (2 × 150 mL), and the combined organic layers were washed with H2O (50 mL), dried (Na2SO4), and concentrated under reduced pressure. The crude product was purified by column chromatography (silica gel, 10–15% EtOAc–hexane) to give a white solid; yield: 0.71 g (60%); mp 156–157 °C. 1H NMR (400 MHz, CDCl3): δ = 9.05 (s, 1 H), 8.85 (d, J = 9.2 Hz, 1 H), 8.35 (d, J = 2.5 Hz, 1 H), 8.23 (dd, J = 9.2, 2.5 Hz, 1 H), 7.97 (d, J = 2.6 Hz, 1 H), 7.55 (dd, J = 8.7, 2.6 Hz, 1 H), 7.18 (d, J = 8.7 Hz, 1 H), 2.40 (s, 3 H). 13C NMR (126 MHz, CDCl3): δ = 168.3, 162.2, 146.4, 143.4, 140.1, 133.2, 132.4, 130.6, 128.1, 125.1, 124.8, 123.8, 122.3, 120.7, 21.3. HRMS (ESI): m/z [M – H]+ calcd for C15H9Cl2N2O5: 366.98940; found: 366.99077.