CoChat
Sign Up
Cited by 5Enzyme Catalysis and ImmobilizationSulfur-Based Synthesis TechniquesStructural and Chemical Analysis of Organic and Inorganic Compounds

The DOI matches its Crossref record; the references it cites are not checked yet.

Biocatalytic synthesis of oxa(thia)diazole aryl thioethers

Open access
Mottaghi Amlashi, Donya, Mobini, Sepideh, Shahedi, Mansour, Habibi, Zohreh, Bavandi, Hossein, Yousefi, Maryam·2024·Scientific Reports
DOI 10.1038/s41598-024-70239-3PMC PMC11341560
Open this paper in CoChat — free accountOpen PDF

Abstract

A novel approach for the synthesis of 1,3,4-oxa(thia)diazole aryl thioethers through a biocatalytic strategy has been introduced. By leveraging Myceliophthora thermophila laccase (Novozym 51003) as a catalyst, catechol undergoes oxidation to ortho-quinone, facilitating subsequent 1,4-thia-Michael addition reactions. The method offers efficiency and mild reaction conditions, demonstrating promise for sustainable synthesis pathways in organic chemistry. Using this approach, 13 new derivatives of 2,5-disubstituted-1,3,4-oxa(thia)diazole aryl thioethers, with a yield of 46-94%, were synthesized.

Overview

The claims and statistics of this paper haven’t been checked yet.

Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.

A few free checks a day · papers already verified open instantly · results are public

Integrity signals

Registry

Crossref · 10.1038/s41598-024-70239-3

Cites

Statistics

Figures

Figure 1 Structures of some biologically active compounds containing 1,3,4-oxa(thia)diazole thioether scaffolds.
Figure 1 Structures of some biologically active compounds containing 1,3,4-oxa(thia)diazole thioether scaffolds.CC BY-NC-ND · PubMed Central
Figure 2 Previous works and this work.
Figure 2 Previous works and this work.CC BY-NC-ND · PubMed Central
Figure 3 The gram scale reaction for compound 3a.
Figure 3 The gram scale reaction for compound 3a.CC BY-NC-ND · PubMed Central
Figure 4 Proposed mechanism.
Figure 4 Proposed mechanism.CC BY-NC-ND · PubMed Central

Verification

Claims the paper makes

The claims and statistics of this paper haven’t been checked yet.

Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.

A few free checks a day · papers already verified open instantly · results are public

Self-check

Percentages, sums and reported differences re-computed from the paper’s own numbers.

The self-check needs the paper’s full text.

Citations

The citation lists haven’t been fetched yet

References 74 · Cited by 5

Research works printed but not linked: 76

  1. Ram, V. J., Sethi, A., Nath, M. & Pratap, R. The Chemistry of Heterocycles: Nomenclature and Chemistry of Three to Five Membered Heterocycles (Elsevier, 2019).
  2. Pearce, S. The importance of heterocyclic compounds in anti-cancer drug design. Drug Discov. 2017, 67 (2017).
  3. Arunachalapandi, M. & Roopan, S. M. Ultrasound/visible lightmediated synthesis of N-heterocycles using g-C3N4/Cu3TiO4 as sonophotocatalyst. Res. Chem. Intermed. 47, 3363–3378 (2021). · DOI
  4. Sompalle, R. & Roopan, S. M. Microwave assisted synthesis of ring junction heterocyclic antioxidants. Res. Chem. Intermed. 42, 5353–5366 (2016). · DOI
  5. Manjupriya, R. & Roopan, S. M. Carbon dots-based catalyst for various organic transformations. J. Mater. Sci. 56, 17369–17410 (2021). · DOI
  6. Li, Y., Geng, J., Liu, Y., Yu, S. & Zhao, G. Thiadiazole—A promising structure in medicinal chemistry. ChemMedChem 8, 27–41 (2013). · DOI
  7. Liu, Y. et al. Fabrication of magnetic amino-functionalized nanoparticles for S-arylation of heterocyclic thiols. RSC Adv. 4, 48980–48985 (2014). · DOI
  8. Desai, N. et al. Synthesis, biological evaluation and molecular docking study of some novel indole and pyridine based 1, 3, 4-oxadiazole derivatives as potential antitubercular agents. Bioorg. Med. Chem. Lett. 26, 1776–1783 (2016). · DOI
  9. Ladani, G. G. & Patel, M. P. Novel 1, 3, 4-oxadiazole motifs bearing a quinoline nucleus: Synthesis, characterization and biological evaluation of their antimicrobial, antitubercular, antimalarial and cytotoxic activities. New J. Chem. 39, 9848–9857 (2015). · DOI
  10. Fioravanti, R. et al. Synthesis and biological evaluation of N-substituted-3, 5-diphenyl-2-pyrazoline derivatives as cyclooxygenase (COX-2) inhibitors. Eur. J. Med. Chem. 45, 6135–6138 (2010). · DOI
  11. Bekhit, A. A., Ashour, H. M., Ghany, Y. S. A., Bekhit, A.E.-D.A. & Baraka, A. Synthesis and biological evaluation of some thiazolyl and thiadiazolyl derivatives of 1H-pyrazole as anti-inflammatory antimicrobial agents. Eur. J. Med. Chem. 43, 456–463 (2008). · DOI
  12. Ahmad, M., Siddiqui, H. L., Zia-ur-Rehman, M. & Parvez, M. Anti-oxidant and anti-bacterial activities of novel N′-arylmethylidene-2-(3, 4-dimethyl-5, 5-dioxidopyrazolo [4, 3-c][1, 2] benzothiazin-2 (4H)-yl) acetohydrazides. Eur. J. Med. Chem. 45, 698–704 (2010). · DOI
  13. Neissari, N. et al. Biocatalytic synthesis of oxadiazole thioethers and evaluation of their antitumor activity. Org. Biomol. Chem. 21, 4846–4853 (2023). · DOI
  14. Khan, M.-U.-H., Akhtar, T., Al-Masoudi, N., Stoeckli-Evans, H. & Hameed, S. Synthesis, crystal structure and anti-HIV activity of 2-adamantyl/adamantylmethyl-5-aryl-1, 3, 4-oxadiazoles. Med. Chem. 8, 1190–1197 (2012).
  15. Zhang, K. et al. Synthesis and antitumor activities of novel hybrid molecules containing 1, 3, 4-oxadiazole and 1, 3, 4-thiadiazole bearing Schiff base moiety. Bioorg. Med. Chem. Lett. 24, 5154–5156 (2014). · DOI
  16. Yan, L. et al. Synthesis of N-pyrimidin [1, 3, 4] oxadiazoles and N-pyrimidin [1, 3, 4]-thiadiazoles from 1, 3, 4-oxadiazol-2-amines and 1, 3, 4-thiadiazol-2-amines via Pd-catalyzed heteroarylamination. Tetrahedron Letters 60, 1359–1362 (2019). · DOI
  17. Karabanovich, G. et al. Development of 3, 5-dinitrobenzylsulfanyl-1, 3, 4-oxadiazoles and thiadiazoles as selective antitubercular agents active against replicating and nonreplicating Mycobacterium tuberculosis. J. Med. Chem. 59, 2362–2380 (2016). · DOI
  18. Hamama, W. S., Gouda, M. A., Badr, M. H. & Zoorob, H. H. Synthesis, antioxidant, and antitumor evaluation of certain new N-substituted-2-amino-1, 3, 4-thiadiazoles. Med. Chem. Res. 22, 3556–3565 (2013). · DOI
  19. Khan, I. et al. Synthesis of benzimidazole based thiadiazole and carbohydrazide conjugates as glycogen synthase kinase-3β inhibitors with anti-depressant activity. Bioorg. Med. Chem. Lett. 26, 4020–4024 (2016). · DOI
  20. Pattan, S. et al. Synthesis and evaluation of some novel 1, 3, 4-thiadiazoles for antidiabetic activity. ChemInform 42, 30 (2011). · DOI
  21. Er, M. et al. Synthesis, characterization, preliminary SAR and molecular docking study of some novel substituted imidazo [2, 1-b][1, 3, 4] thiadiazole derivatives as antifungal agents. Med. Chem. Res. 26, 615–630 (2017). · DOI
  22. Dunbar, K. L., Scharf, D. H., Litomska, A. & Hertweck, C. Enzymatic carbon–sulfur bond formation in natural product biosynthesis. Chem. Rev. 117, 5521–5577 (2017). · DOI
  23. Ilardi, E. A., Vitaku, E. & Njardarson, J. T. Data-mining for sulfur and fluorine: An evaluation of pharmaceuticals to reveal opportunities for drug design and discovery: Miniperspective. J. Med. Chem. 57, 2832–2842 (2014). · DOI
  24. Liu, L. et al. SAR of 3, 4-Dihydropyrido [3, 2-d] pyrimidone p38 Inhibitors. Bioorg. Med. Chem. Lett. 13, 3979–3982 (2003). · DOI
  25. Zhao, C., Rakesh, K., Ravidar, L., Fang, W.-Y. & Qin, H.-L. Pharmaceutical and medicinal significance of sulfur (SVI)-Containing motifs for drug discovery: A critical review. Eur. J. Med. Chem. 162, 679–734 (2019). · DOI
  26. De Martino, G. et al. Arylthioindoles, potent inhibitors of tubulin polymerization. J. Med. Chem. 47, 6120–6123 (2004). · DOI
  27. Alcaraz, M.-L. et al. Efficient syntheses of AZD4407 via thioether formation by nucleophilic attack of organometallic species on sulphur. Org. Process Res. Dev. 9, 555–569 (2005). · DOI
  28. Nielsen, S. F., Nielsen, E. Ø., Olsen, G. M., Liljefors, T. & Peters, D. Novel potent ligands for the central nicotinic acetylcholine receptor: Synthesis, receptor binding, and 3D-QSAR analysis. J. Med. Chem. 43, 2217–2226 (2000). · DOI
  29. Samanta, S., Ray, S., Ghosh, A. B. & Biswas, P. 3, 6-Di (pyridin-2-yl)-1, 2, 4, 5-tetrazine (pytz) mediated metal-free mild oxidation of thiols to disulfides in aqueous medium. RSC Adv. 6, 39356–39363 (2016). · DOI
  30. El-Masry, R. M., Kadry, H. H., Taher, A. T. & Abou-Seri, S. M. Comparative study of the synthetic approaches and biological activities of the bioisosteres of 1, 3, 4-oxadiazoles and 1, 3, 4-thiadiazoles over the past decade. Molecules 27, 2709 (2022). · DOI
  31. Yu, Q. et al. Novel 1, 3, 4-oxadiazole hybrids of 3-n-butylphthalide derivatives as potential anti-ischemic stroke agents. Bioorg. Chem. 143, 107034 (2024). · DOI
  32. Yonova, I. M., Osborne, C. A., Morrissette, N. S. & Jarvo, E. R. Diaryl and heteroaryl sulfides: Synthesis via sulfenyl chlorides and evaluation as selective anti-breast-cancer agents. J. Org. Chem. 79, 1947–1953 (2014). · DOI
  33. Zhang, F. et al. Synthesis, molecular modeling and biological evaluation of N-benzylidene-2-((5-(pyridin-4-yl)-1, 3, 4-oxadiazol-2-yl) thio) acetohydrazide derivatives as potential anticancer agents. Bioorg. Med. Chem. 22, 468–477 (2014). · DOI
  34. Polkam, N., Malthum, S., Anireddy, J., Brahma, U. & Naidu-Vegi, G. Design, synthesis, and anticancer evaluation of new 1, 3, 4-oxadiazole thioether derivatives. Russian Chem. Bull. 70, 580–584 (2021). · DOI
  35. Boddapati, S. M., Talari, S., Kola, A. E. & Chalapaka, B. Synthesis of 2-aryl-5-(arylsulfonyl)-1, 3, 4-oxadiazoles as potent antibacterial andantioxidant agents. Turk. J. Chem. 46, 766–776 (2022). · DOI
  36. Hamoud, M. M. et al. Design and synthesis of novel 1, 3, 4-oxadiazole and 1, 2, 4-triazole derivatives as cyclooxygenase-2 inhibitors with anti-inflammatory and antioxidant activity in LPS-stimulated RAW264. 7 macrophages. Bioorg. Chem. 124, 105808 (2022). · DOI
  37. Migita, T. et al. The palladium catalyzed nucleophilic substitution of aryl halides by thiolate anions. Bull. Chem. Soc. Jpn. 53, 1385–1389 (1980). · DOI
  38. Percec, V., Bae, J.-Y. & Hill, D. H. Aryl mesylates in metal catalyzed homocoupling and cross-coupling reactions. 2. Suzuki-type nickel-catalyzed cross-coupling of aryl arenesulfonates and aryl mesylates with arylboronic acids. J. Org. Chem. 60, 6895–6903 (1995). · DOI
  39. Zhang, Y., Ngeow, K. C. & Ying, J. Y. The first N-heterocyclic carbene-based nickel catalyst for C− S coupling. Org. Lett. 9, 3495–3498 (2007). · DOI
  40. Ranjit, S. et al. Copper-mediated C-H activation/C–S cross-coupling of heterocycles with thiols. J. Org. Chem. 76, 8999–9007 (2011). · DOI
  41. Dai, C., Xu, Z., Huang, F., Yu, Z. & Gao, Y.-F. Lewis acid-catalyzed, copper (II)-mediated synthesis of heteroaryl thioethers under base-free conditions. J. Org. Chem. 77, 4414–4419 (2012). · DOI
  42. Petrosyan, A., Ayvazyan, A., Ghochikyan, T. & Galstyan, A. Ligand-free Cu (0) catalyzed C-S cross-coupling ullmann-type reaction: S-arylation of 5, 4-disubstituted-2, 4-dihydro-3h-1, 2, 4-triazole-3-thiones. Eur. J. Org. Chem. 2024, e202400199 (2024). · DOI
  43. Wong, Y.-C., Jayanth, T. T. & Cheng, C.-H. Cobalt-catalyzed aryl−sulfur bond formation. Org. Lett. 8, 5613–5616 (2006). · DOI
  44. Correa, A., Carril, M. & Bolm, C. Iron-catalyzed Sonogashira reactions. Angew. Chem. Int. Ed. 47, 2880–2883 (2008). · DOI
  45. Correa, A., Mancheño, O. G. & Bolm, C. Iron-catalysed carbon–heteroatom and heteroatom–heteroatom bond forming processes. Chem. Soc. Rev. 37, 1108–1117 (2008). · DOI
  46. Reddy, V. P., Swapna, K., Kumar, A. V. & Rao, K. R. Indium-catalyzed C− S cross-coupling of aryl halides with thiols. J. Org. Chem. 74, 3189–3191 (2009). · DOI
  47. Reddy, V. P., Kumar, A. V., Swapna, K. & Rao, K. R. Nano indium oxide as a recyclable catalyst for C− S cross-coupling of thiols with aryl halides under ligand free conditions. Org. Lett. 11, 1697–1700 (2009). · DOI
  48. Mispelaere-Canivet, C., Spindler, J.-F., Perrio, S. & Beslin, P. Pd2 (dba) 3/Xantphos-catalyzed cross-coupling of thiols and aryl bromides/triflates. Tetrahedron 61, 5253–5259 (2005). · DOI
  49. Itoh, T. & Mase, T. A general palladium-catalyzed coupling of aryl bromides/triflates and thiols. Org. Lett. 6, 4587–4590 (2004). · DOI
  50. Zheng, N., McWilliams, J. C., Fleitz, F. J., Armstrong, J. D. & Volante, R. Palladium-catalyzed synthesis of aryl sulfides from aryl triflates. J. Org. Chem. 63, 9606–9607 (1998). · DOI
  51. Savarin, C., Srogl, J. & Liebeskind, L. S. A mild, nonbasic synthesis of thioethers. The copper-catalyzed coupling of boronic acids with N-thio (alkyl, aryl, heteroaryl) imides. Org. Lett. 4, 4309–4312 (2002). · DOI
  52. Herradura, P. S., Pendola, K. A. & Guy, R. K. Copper-mediated cross-coupling of aryl boronic acids and alkyl thiols. Org. Lett. 2, 2019–2022 (2000). · DOI
  53. Louie, J. & Hartwig, J. F. Transmetalation, involving organotin aryl, thiolate, and amide compounds. An unusual type of dissociative ligand substitution reaction. J. Am. Chem. Soc. 117, 11598–11599 (1995). · DOI
  54. Jha, K. K. et al. Design, synthesis and biological evaluation of 1, 3, 4-oxadiazole derivatives. Eur. J. Med. Chem. 45, 4963–4967 (2010). · DOI
  55. Parikh, P. K., Marvaniya, H. M. & Sen, D. J. Synthesis and biological evaluation of 1, 3, 4-oxadiazole derivatives as potential antibacterial and antifungal agents. Int. J. Drug Dev. Res. 3, 248–255 (2011).
  56. Rafique, J., Saba, S., Rosario, A. R., Zeni, G. & Braga, A. L. K 2 CO 3-mediated, direct C-H bond selenation and thiolation of 1, 3, 4-oxadiazoles in the absence of metal catalyst: An eco-friendly approach. RSC Adv. 4, 51648–51652 (2014). · DOI
  57. An, Y. et al. Efficient formation of C-S bond using heterocyclic thiones and arynes. Tetrahedron 79, 131829 (2021). · DOI
  58. Wu, Q., Xu, J. M., Xia, L., Wang, J. L. & Lin, X. F. Promiscuous zinc-dependent acylase-mediated one-pot synthesis of monosaccharide-containing pyrimidine derivatives in organic medium. Adv. Synth. Catal. 351, 1833–1841 (2009). · DOI
  59. Li, C. et al. Promiscuous protease-catalyzed aldol reactions: A facile biocatalytic protocol for carbon–carbon bond formation in aqueous media. J. Biotechnol. 150, 539–545 (2010). · DOI
  60. Baldrian, P. Fungal laccases–occurrence and properties. FEMS Microbiol. Rev. 30, 215–242 (2006). · DOI
  61. Abdel-Mohsen, H. T., Conrad, J. R. & Beifuss, U. Laccase-catalyzed domino reaction between catechols and 6-substituted 1, 2, 3, 4-tetrahydro-4-oxo-2-thioxo-5-pyrimidinecarbonitriles for the synthesis of pyrimidobenzothiazole derivatives. J. Org. Chem. 78, 7986–8003 (2013). · DOI
  62. Wellington, K. W., Bokako, R., Raseroka, N. & Steenkamp, P. A one-pot synthesis of 1, 4-naphthoquinone-2, 3-bis-sulfides catalysed by a commercial laccase. Green Chem. 14, 2567–2576 (2012). · DOI
  63. Cannatelli, M. D. & Ragauskas, A. J. Ecofriendly syntheses of phenothiazones and related structures facilitated by laccase–a comparative study. Tetrahedron Lett. 57, 3749–3753 (2016). · DOI
  64. Witayakran, S. & Ragauskas, A. J. Synthetic applications of laccase in green chemistry. Adv. Synth. Catal. 351, 1187–1209 (2009). · DOI
  65. González-Sabín, J. et al. Laccase-catalysed biotransformation of collismycin derivatives. A novel enzymatic approach for the cleavage of oximes. Green Chem. 18, 989–994 (2016). · DOI
  66. Llevot, A., Grau, E., Carlotti, S., Grelier, S. & Cramail, H. Selective laccase-catalyzed dimerization of phenolic compounds derived from lignin: Towards original symmetrical bio-based (bis) aromatic monomers. J. Mol. Catal. B: Enzym. 125, 34–41 (2016). · DOI
  67. Emirdağ-Öztürk, S., Hajdok, S., Conrad, J. & Beifuss, U. Laccase-catalyzed reaction of 3-tert-butyl-1H-pyrazol-5 (4H)-one with substituted catechols using air as an oxidant. Tetrahedron 69, 3664–3668 (2013). · DOI
  68. Hahn, V., Mikolasch, A., Kuhlisch, C. & Schauer, F. Laccase-mediated multi-step homo-and heteromolecular reactions of ortho-dihydroxylated aromatic compounds and mono-or diaminated substances resulting in CC, CO and CN bonds. J. Mol. Catal. B: Enzym. 122, 56–63 (2015). · DOI
  69. Abdel-Mohsen, H. T., Conrad, J. & Beifuss, U. Laccase-catalyzed synthesis of catechol thioethers by reaction of catechols with thiols using air as an oxidant. Green Chem. 16, 90–95 (2014). · DOI
  70. Witayakran, S. & Ragauskas, A. J. One-pot synthesis of 1, 4-naphthoquinones and related structures with laccase. Green Chem. 9, 475–480 (2007). · DOI
  71. Abdel-Mohsen, H., Conrad, J., Harms, K., Nohr, D. & Beifuss, U. Laccase-catalyzed green synthesis and cytotoxic activity of novel pyrimidobenzothiazoles and catechol thioethers. RSC Adv. 7, 17427–17441 (2017). · DOI
  72. Hahn, V. et al. Ring-closure mechanisms mediated by laccase to synthesize phenothiazines, phenoxazines, and phenazines. ACS Omega 5, 14324–14339 (2020). · DOI
  73. Eggert, C., Temp, U., Dean, J. F. & Eriksson, K.-E.L. Laccase-mediated formation of the phenoxazinone derivative, cinnabarinic acid. FEBS Lett. 376, 202–206 (1995). · DOI
  74. Cannatelli, M. D. & Ragauskas, A. J. Laccase-catalyzed synthesis of 2, 3-ethylenedithio-1, 4-quinones. J. Mol. Catal. B: Enzym. 119, 85–89 (2015). · DOI
  75. Shahedi, M. et al. Diarylation of thiazolopyrimidines by laccase and their in vitro evaluation as antitumor agents. Sci. Rep. 12, 22326 (2022). · DOI
  76. Shahedi, M. et al. Biocatalytic stereoselective synthesis of pyrrolidine-2, 3-diones containing all-carbon quaternary stereocenters. Org. Biomol. Chem. 21, 2742–2747 (2023). · DOI

Metadata

Authors
Mottaghi Amlashi, D., Mobini, S., Shahedi, M., Habibi, Z., Bavandi, H., & Yousefi, M.
Affiliations
  • Shahid Beheshti University (IR)
  • Academic Center for Education, Culture and Research (IR)
Corresponding author
Yousefi, Maryam
ORCID
Venue
Scientific Reports
Publisher
Springer Science and Business Media LLC
Published
2024-08-22
Volume
14
Issue
1
Pages
19468-19468
ISSN
2045-2322 (ISSN-L)
DOI
10.1038/s41598-024-70239-3
PMC
PMC11341560
OpenAlex
W4401818575
Cited by
5
References
74
Citations by year
2026: 3 · 2025: 2
FWCI
0.68
Type
journal article
Language
en
Open access
Licence
Locations
  • Scientific Reports (publishedVersion, cc-by-nc-nd)
  • PubMed Central (publishedVersion, cc-by-nc-nd)
  • PubMed (publishedVersion)
  • DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion)
Topics
  • Life Sciences › Biochemistry, Genetics and Molecular Biology › Molecular Biology › Enzyme Catalysis and Immobilization
  • Physical Sciences › Chemistry › Organic Chemistry › Sulfur-Based Synthesis Techniques
  • Physical Sciences › Chemistry › Organic Chemistry › Structural and Chemical Analysis of Organic and Inorganic Compounds
Keywords
enzymatic synthesis, catechol oxidation, ortho-quinones, heterocyclic synthesis, sustainable organic synthesis

About these checks

Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.

Statistics and arithmetic are recomputed, not judged.

Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.

What counts as a claim ›How we measure confidence ›How we check this ›

Are you an author, or do you see a problem with this page? Request a review

How to cite

Cite CoChat for the checks on this page, and the paper for its own findings.

This page
CoChat. (2026). Citation check: Biocatalytic synthesis of oxa(thia)diazole aryl thioethers. https://app.cochat.ai/papers/10.1038/s41598-024-70239-3
The paper
Mottaghi Amlashi, D., Mobini, S., Shahedi, M., Habibi, Z., Bavandi, H., & Yousefi, M. (2024). Biocatalytic synthesis of oxa(thia)diazole aryl thioethers. Scientific Reports. https://doi.org/10.1038/s41598-024-70239-3