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image of Nickel-Catalyzed Coupling Reaction of Arylboronic Acid with Methyl Dithiocarbamates for the Synthesis of Thioamides

Abstract

This study aimed to carry out highly efficient and simple cross-coupling reactions of arylboronic acid with methyl dithiocarbamates for the synthesis of thioamide derivatives using Ni(acac)(5 mol%)/TFP(5 mol%) as a catalyst. Under the optimized reaction conditions, the coupling reaction between arylboronic acid with methyl dithiocarbamates was carried out smoothly, and thioamides were obtained with 27-85% isolated yields. Furthermore, dithiocarbamate methyl esters with allyl, cyano, and acid-sensitive ketal functional groups were successfully coupled with phenylboronic acid to produce the desired product, thioamides, with a yield of 27-69%. Aromatic boronic acids with methoxy or formyl groups on the benzene ring were found to be compatible in this reaction system, and the corresponding thioamides were obtained with an isolated yield of 31-43%. A thioamide with 1-(bis(4-fluorophenyl)methyl)piperazine structural units was prepared with a yield of 65%, which has the potential biological activity. However, this reaction system did not achieve satisfactory results for methyl 1-imidazole-1-carbodithioate. The structures of all the target compounds were confirmed by melting point determination, HMRS, 1H NMR, and 13-CNMR. The broad functional group tolerance and consistent high efficiency at gram-scale synthesis make this protocol a potentially practical approach for producing thioamide derivatives. The method avoids the use of expensive transition metals, such as Pd, Ir, or Rh, and has the advantage of simple operation.

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2025-06-27
2025-11-14

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References

  1. Mahanta N. Szantai-Kis D.M. Petersson E.J. Mitchell D.A. ACS Chem. Biol. 2019 14 2 142 163 10.1021/acschembio.8b01022 30698414
    [Google Scholar]
  2. Goldberg J.M. Chen X. Meinhardt N. Greenbaum D.C. Petersson E.J. J. Am. Chem. Soc. 2014 136 5 2086 2093 10.1021/ja412297x 24472041
    [Google Scholar]
  3. Czepa W. Witomska S. Samorì P. Ciesielski A. Small Sci. 2023 3 5 2300013 10.1002/smsc.202300013 40213318
    [Google Scholar]
  4. Watanabe H. Kamigaito M. J. Am. Chem. Soc. 2023 145 20 10948 10953 10.1021/jacs.3c01796 37079587
    [Google Scholar]
  5. Kapanda C.N. Muccioli G.G. Labar G. Draoui N. Lambert D.M. Poupaert J.H. Med. Chem. Res. 2009 18 4 243 254 10.1007/s00044‑008‑9123‑2
    [Google Scholar]
  6. Yazaki R. Kumagai N. Shibasaki M. Org. Lett. 2011 13 5 952 955 10.1021/ol102998w 21291204
    [Google Scholar]
  7. Simonetti S.O. Larghi E.L. Bracca A.B.J. Kaufman T.S. Nat. Prod. Rep. 2013 30 7 941 969 10.1039/c3np70014c 23719995
    [Google Scholar]
  8. Jagodziński T.S. Chem. Rev. 2003 103 1 197 228 10.1021/cr0200015 12517184
    [Google Scholar]
  9. Hurd R.N. DeLaMater G. Chem. Rev. 1961 61 1 45 86 10.1021/cr60209a003
    [Google Scholar]
  10. Wahab Khan M. Jahangir Alam M. Rashid M.A. Chowdhury R. Bioorg. Med. Chem. 2005 13 16 4796 4805 10.1016/j.bmc.2005.05.009 15964760
    [Google Scholar]
  11. Banigé M. Polak M. Luton D. Benachi A. Biran V. Mokhtari M. Boithias C. Champion V. Desfrere L. Ville Y. Jarreau P-H. Dommergues M. Brioude F. Mandelbrot L. Mitanchez D. J. Pediatr. 2018 197 249 254.e1 10.1016/j.jpeds.2018.01.071 29605392
    [Google Scholar]
  12. Phan H.A.T. Chang Y. Eaton S.A. Petersson E. J. Chem. Commun (Camb) 2024 60 89 13075 13078 10.1039/D4CC03309D 39439401
    [Google Scholar]
  13. Bayram K. Kiskan B. Yagci Y. Polym. Chem. 2021 12 4 534 544 10.1039/D0PY01381A
    [Google Scholar]
  14. Ilkin V.G. Filimonov V.O. Utepova I.A. Beryozkina T.V. Slepukhin P.A. Tumashov A.A. Dehaen W. Bakulev V.A. Org. Chem. Front. 2024 11 13 3537 3545 10.1039/D3QO02025H
    [Google Scholar]
  15. Priebbenow D.L. Bolm C. Chem. Soc. Rev. 2013 42 19 7870 7880 10.1039/c3cs60154d 23793793
    [Google Scholar]
  16. Liu J. Zhao S. Yan X. Zhang Y. Zhao S. Zhuo K. Yue Y. Asian J. Org. Chem. 2017 6 12 1764 1768 10.1002/ajoc.201700532
    [Google Scholar]
  17. Jin H. Chen X. Qian C. Ge X. Zhou S. Eur. J. Org. Chem. 2021 2021 23 3403 3406 10.1002/ejoc.202100588
    [Google Scholar]
  18. Zhan Z. Luo N. Ma H. He J. Lu G. Cui X. Huang G. ChemistrySelect 2019 4 45 13388 13391 10.1002/slct.201903512
    [Google Scholar]
  19. Shibahara F. Sugiura R. Murai T. Org. Lett. 2009 11 14 3064 3067 10.1021/ol9010882 19534478
    [Google Scholar]
  20. Li G. Xing Y. Zhao H. Zhang J. Hong X. Szostak M. Angew. Chem. Int. Ed. 2022 61 16 e202200144 10.1002/anie.202200144 35122374
    [Google Scholar]
  21. Wei J. Li Y. Jiang X. Org. Lett. 2016 18 2 340 343 10.1021/acs.orglett.5b03541 26734786
    [Google Scholar]
  22. Gupta A. Vankar J.K. Jadav J.P. Gururaja G.N. J. Org. Chem. 2022 87 5 2410 2420 10.1021/acs.joc.1c02307 35133151
    [Google Scholar]
  23. Xu K. Li Z. Cheng F. Zuo Z. Wang T. Wang M. Liu L. Org. Lett. 2018 20 8 2228 2231 10.1021/acs.orglett.8b00573 29600861
    [Google Scholar]
  24. Guntreddi T. Vanjari R. Singh K.N. Org. Lett. 2014 16 14 3624 3627 10.1021/ol501482g 24978059
    [Google Scholar]
  25. Saito M. Murakami S. Nanjo T. Kobayashi Y. Takemoto Y. J. Am. Chem. Soc. 2020 142 18 8130 8135 10.1021/jacs.0c03256 32315161
    [Google Scholar]
  26. Do T.H. Phaenok S. Soorukram D. Modjinou T. Grande D. Nguyen T.T.T. Nguyen T.B. Org. Lett. 2023 25 34 6322 6327 10.1021/acs.orglett.3c02247 37606344
    [Google Scholar]
  27. Mandal S. Jain A. Panda T.K. RSC Sustainability 2024 2 8 2249 2255 10.1039/D4SU00206G
    [Google Scholar]
  28. Peng L. Ma L. Ran Y. Chen Y. Zeng Z. Tetrahedron Lett. 2021 74 153092 10.1016/j.tetlet.2021.153092
    [Google Scholar]
  29. Wang X. Xu S. Tang Y. Lear M.J. He W. Li J. Nat. Commun. 2023 14 1 4626 10.1038/s41467‑023‑40334‑6 37532721
    [Google Scholar]
  30. Wu J.W. Wu Y.D. Dai J.J. Xu H.J. Adv. Synth. Catal. 2014 356 11-12 2429 2436 10.1002/adsc.201400068
    [Google Scholar]
  31. Zhang J. Zhao H. Li G. Zhu X. Shang L. He Y. Liu X. Ma Y. Szostak M. Org. Biomol. Chem. 2022 20 30 5981 5988 10.1039/D2OB00412G 35441645
    [Google Scholar]
  32. Gao Y. Chai F. Liu C. New J. Chem. 2024 48 46 19496 19500 10.1039/D4NJ03032J
    [Google Scholar]
  33. Patra D. Saha A. Org. Chem. Front. 2023 10 7 1686 1693 10.1039/D3QO00032J
    [Google Scholar]
  34. Patra D. Saha A. Org. Chem. Front. 2024 11 4 1150 1156 10.1039/D3QO01921G
    [Google Scholar]
  35. Xu X. Qiu R. Chen S. Li Y. Chen J. Su L. Tang Z. Au C.T. Synlett 2016 27 16 2339 2344 10.1055/s‑0035‑1562509
    [Google Scholar]
  36. Wang X. Ji M. Lim S. Jang H.Y. J. Org. Chem. 2014 79 15 7256 7260 10.1021/jo501378v 24993111
    [Google Scholar]
  37. Devi P.S. Saranya S. Anilkumar G. Catal. Sci. Technol. 2024 14 9 2320 2351 10.1039/D4CY00034J
    [Google Scholar]
  38. Behmagham F. Mustafa M.A. Saraswat S.K. Khalaf K.A. Kaur M. Ghildiyal P. Vessally E. RSC Advances 2024 14 13 9184 9199 10.1039/D4RA00487F 38505389
    [Google Scholar]
  39. Kadu B.S. Catal. Sci. Technol. 2021 11 4 1186 1221 10.1039/D0CY02059A
    [Google Scholar]
  40. Kommoju A. Snehita K. Sowjanya K. Mukkamala S.B. Padala K. Chem. Commun. (Camb.) 2024 60 68 8946 8977 10.1039/D4CC02914C 39086201
    [Google Scholar]
  41. Han F.S. Chem. Soc. Rev. 2013 42 12 5270 5298 10.1039/c3cs35521g 23460083
    [Google Scholar]
  42. Dutta S. Saha A. Tetrahedron Lett. 2020 61 41 152382 10.1016/j.tetlet.2020.152382
    [Google Scholar]
  43. Mondal M. Saha A. Org. Biomol. Chem. 2022 20 17 3491 3494 10.1039/D2OB00315E 35411902
    [Google Scholar]
  44. Jiang X. Xiao H. Jia X. Pu J. Han L. Li Q. New J. Chem. 2023 47 29 14078 14094 10.1039/D3NJ02026F
    [Google Scholar]
  45. Liang M. Pu J. Jia X. Han L. Li Q. Lett. Org. Chem. 2024 21 2 116 123 10.2174/1570178620666230821142342
    [Google Scholar]
  46. Xiao H.L. Zhang G. Luo R.Q. Li Q.H. Tetrahedron 2022 103 132549 10.1016/j.tet.2021.132549
    [Google Scholar]
  47. Wu K. Wu C. Jia X.Y. Zhou L. Li Q.H. RSC Advances 2022 12 21 13314 13318 10.1039/D2RA02127G 35520111
    [Google Scholar]
  48. Zhang Z. Jia X. Pu J. Han L. Hou J. Li Q. Lett. Org. Chem. 2024 21 12 1055 1063 10.2174/0115701786298931240408083720
    [Google Scholar]
  49. Zhang Z.H. Pu J.X. Jia X.Y. Hou J.S. Han L.R. Wu C. Li Q.H. J. Organomet. Chem. 2024 1014 123192 10.1016/j.jorganchem.2024.123192
    [Google Scholar]
  50. Li Q. Luo R. Wu C. Xiao H. Guo S. Zhang Z. Huang Z. Zhou L. Youji Huaxue 2021 41 4 1489 1497 10.6023/cjoc202009029
    [Google Scholar]
  51. Pu J.X. Hou J.S. Han L.R. Jia X.Y. Li Q.H. Tetrahedron 2024 162 134089 10.1016/j.tet.2024.134089
    [Google Scholar]
  52. Mei Q. Li Q. Youji Huaxue 2024 44 2 398 408 10.6023/cjoc202308008
    [Google Scholar]
  53. Jia X. Pu J. Han L. Li Q. Youji Huaxue 2024 44 1 18 40 10.6023/cjoc202306003
    [Google Scholar]
  54. Pu J. Jia X. Han L. Li Q. Youji Huaxue 2023 43 8 2591 2613 10.6023/cjoc202302002
    [Google Scholar]
  55. Ding Y. Li Q. Zhao Z. Yang X. Chen F. Youji Huaxue 2017 37 12 3282 3288 10.6023/cjoc201707001
    [Google Scholar]
  56. Monteith J.J. Scotchburn K. Mills L.R. Rousseaux S.A.L. Org. Lett. 2022 24 2 619 624 10.1021/acs.orglett.1c04074 34978834
    [Google Scholar]
  57. Kale A.D. Tayade Y.A. Mahale S.D. Patil R.D. Dalal D.S. Tetrahedron 2019 75 41 130575 10.1016/j.tet.2019.130575
    [Google Scholar]
  58. Jin H. Ge X. Zhou S. Eur. J. Org. Chem. 2021 2021 44 6015 6021 10.1002/ejoc.202101013
    [Google Scholar]
  59. Murai T. Mutoh Y. Ohta Y. Murakami M. J. Am. Chem. Soc. 2004 126 19 5968 5969 10.1021/ja048627v 15137753
    [Google Scholar]
  60. Khatri C.K. Mali A.S. Chaturbhuj G.U. Monatsh. Chem. 2017 148 8 1463 1468 10.1007/s00706‑017‑1944‑6
    [Google Scholar]
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Nickel-Catalyzed Coupling Reaction of Arylboronic Acid with Methyl Dithiocarbamates for the Synthesis of Thioamides
Bentham Science Publishers ; https://doi.org/10.2174/0115701786318561250619115451
/content/journals/loc/10.2174/0115701786318561250619115451
/content/journals/loc/10.2174/0115701786318561250619115451
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  • Article Type:     Research Article
Keywords: methyldithiocarbamates ; Nickel catalyst ; thioamides ; arylboronic acid ; organic synthesis ; cross-coupling reaction

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