SIOC 中文
CJOG
Adv search

Chinese Journal of Organic Chemistry >

0 0

DOI: https://doi.org/10.6023/cjoc202605022

ARTICLE

Transition-Metal-Free Reaction of α-Bromonitriles with Thiosulfonates: Synthesis of α-Sulfonyl-α-(aryl/alkylthio)nitriles

  • Zhang Yuhang ,
  • Yang Yimin ,
  • Jiang Jiajia ,
  • Yao Qiuli ,
  • Huang Yang
Expand
  • Guizhou Provincial Key Laboratory of Innovation and Manufacturing for Pharmaceuticals, School of Pharmacy, Zunyi Medical University, Zunyi, Guizhou 563003

Received date: 2026-05-20

  Revised date: 2026-07-20

  Online published: 2026-08-28

Supported by

Zunyi Medical University (No. F-1119), Natural Science Research Project of Guizhou Provincial Department of Education (No. [2024]334).

Fold

Abstract

We report a transition-metal-free difunctionalization reaction of thiosulfonates with α-bromonitriles, enabling the efficient synthesis of α-sulfonyl-(aryl/alkylthio)nitrile derivatives. In a single step, this protocol simultaneously constructs two distinct carbon-sulfur bonds at the α-position of the cyano group, thereby providing a new approach to all-carbon quaternary centers bearing cyano, sulfonyl, and aryl/alkylthio groups. The method exhibits broad substrate scope and excellent functional-group tolerance: substrates bearing either electron-withdrawing or electron-donating substituents afford the corresponding α-sulfonyl-α-(aryl/alkylthio)nitrile derivatives in moderate to excellent yields. Notably, this protocol features mild reaction conditions, operational simplicity, and high atom economy.

Key words： α-bromonitriles; thiosulfonates; difunctionalization; α-sulfonyl-α-(aryl/alkylthio)nitrile

Cite this article

Zhang Yuhang , Yang Yimin , Jiang Jiajia , Yao Qiuli , Huang Yang . Transition-Metal-Free Reaction of α-Bromonitriles with Thiosulfonates: Synthesis of α-Sulfonyl-α-(aryl/alkylthio)nitriles[J]. Chinese Journal of Organic Chemistry, 0 : 0 . DOI: 10.6023/cjoc202605022

References

[1](a) Chen, L.; Pu, M.-P.; Li, S.-Y.; Sang, V X.-P.; Liu, X.-H.; Wu, Y.-D.; Feng, X.-M.J. Am. Chem. Soc. 2021, 143, 19091-19098.
(b) Wang X.; Wang Y.; Li X.; Yu Z.; Song C.; Du, Y. RSC Med. Chem.2021, 12, 1650.
(c) Tiz, D. B.; Mangiavacchi, F.; Sancineto, L. Phosphorus Sulfur Silicon Relat. Elem. 2026, 1-19.
(d) Flick, A. C., Ding, H. X., Leverett, C. A., Kyne, R. E., Liu, K. K.-C., Fink, S. J., O’ Donnell, C. J. Bioorg. Med. Chem. 2016, 24, 1937-1980.
[2]Donslund A. S.; Neumann K. T.; Corneliussen N. P.; Grove E. K.; Herbstritt D.; Dagsbjerg K.; Skrydstrup, T. Chem. Eur. J.2019, 25, 14359.
[3]Tang S.; Liu C.; Lei A. Chem. Commun.2013, 49, 2442.
[4]Xie J.; Han J.; Liu X.; Yue, H. Org Lett.2026, 28, 2415.
[5]Choi J.; Fu, G. C. J. Am. Chem. Soc.2012, 134, 9102.
[6]Yang Y.; Tang S.; Liu C.; Zhang H.; Sun Z.; Lei, A. Org. Bio. Chem.2011, 9, 5343.
[7]Shimkin K. W.; Gildner P. G.; Watson, D. A. Org. Lett.2016, 18, 988.
[8]Yang J.; Zhang M.; Ban Y.; Hou Z.; Xiao X.; Yao Q.; Huang Y. Org. Lett.2026, 28, 2753.
[9]Wen J.-L.; Guo P.; Pu G.-L.; Man X.-Y.; He, C.-Y. Chin. J. Org. Chem.2025, 45, 4405 (in Chinese).
(温吉林, 郭鹏, 蒲国良, 满雪玉, 贺春阳. 有机化学, 2025, 45, 4405.)
[10](a) Gutarowska B.; Kotynia R.; Bieliński D.; Anyszka R.; Wręczycki J.; Piotrowska M.; Koziróg A.; Berłowska J.; Dziugan P. Materials2019, 12, 2602.
(b) Li C.; Wang Y.; Jiang H.; Wang X. Sensors2020, 20, 3488.
[11](a) Devendar P.; Yang, G.-F. Top. Curr. Chem.2017, 375, 1.
(b) Kaul L.; Süss R.; Zannettino A.; Richter K. iScience2021, 24, 102092.
(c) Cherkasov R. A.; Sofronov A. V.; Martianov Y. M.; Nizamov I. S.; Terenzhev, D. A. Sulfur Silicon Relat. Elem.2011, 186, 1003.
[12](a) Zhou N.; Zeller W.; Krohn M.; Anderson H.; Zhang J.; Onua E.; Kiselyov A. S.; Ramirez J.; Halldorsdottir G.; Andreésson H.; Gurney M. E.; Singh, J. Bioorg. Med. Chem. Lett.2009, 19, 123.
(b) Gangjee A.; Zeng Y.; Talreja T.; McGuire J. J.; Kisliuk R. L.; Queener, S. F. J. Med. Chem.2007, 50, 3046.
(c) Liu G.; Huth J. R.; Olejniczak E. T.; Mendoza R.; DeVries P.; Leitza S.; Reilly E. B.; Okasinski G. F.; Fesik S. W.; von Geldern, T. W. J. Med. Chem.2001, 44, 1202.
(d) Feng M.; Tang B.; Liang S. H.; Jian, X. Curr. Top. Med. Chem.2016, 16, 1200.
[13]Rather S. A.; Athimoolam S.; Ahmed, Q. N. Chem. - Eur. J.2022, 28, e202200822.
[14](a) Tong W.; Gao H.; Yao W.; Liu J.; Wan J.-P. Org. Lett.2026, 28, 4234.
(b) Liu J.; Liang W.; Wan C.; Wan, J.-P. Chin. Chem. Lett.2026, 37, 112202.
(c) Liu, F.; Xu, X.; Wang, X.; Liu, C.; Chen, X.; Sun, K. Chin. J. Org. Chem. 2025, 45, 3903.
(d) Cao, S.; Guo, H.; Zhong, Z.; Chen, D.; Song, W.; Liu, Y.; Wan, J.P. Sci. Adv. 2025, 11, eaea4120.
(e) Chen, L.; Jiang, Z.-T.; Yang, H.; Hu, F.; Xia, Y. Chin. J. Org. Chem. 2025, 45, 2222-2230.
[15](a) Hu A.M.; Tu J.-L.; Luo M.; Yang C.; Guo L.; Xia, W. Org. Chem. Front.2023, 10, 4764.
(b) Wen X.; Li M.; Peng X.; Liu C.; Zhong X.; Tan R.; Jiang H.; Li, J. J. Org. Chem.2024, 89, 14255.
(c) Liu W.; He Y.; Liu Z.-Y.; Li Y. L.; Li Y.; Wu B.-B.; Jin R.-X.; Wang, X.-S. Org. Chem. Front.2023, 10, 2943.
(d) Sharma P.; Jain, N. J. Org. Chem.2019, 84, 13045.
(e) Chen Y.; Wang F.; Liu B.-X.; Rao W.-D.; Wang, S.-Y. Org. Chem. Front.2022, 9, 731.
(f) Fang Y.; Rogge T.; Ackermann L.; Wang S.-Y.; Ji S.-J. Nat. Commun.2018, 9, 2240.
(g) Wang M.-D.; Li Y.-N.; Xiao L.-X.; Zhang R.-H.; Yuan M.; Wang Z.-L.; Zhang X.-G.; Tu H.-Y. Org. Lett.2025, 27, 391.
(h) Liu L.; Wang Q.; Li Y.; Liu M.; Liu B.; Li Q.; Feng K. Org. Lett.2024, 26, 2271.
(i) Wang T.; Zong Y.-Y.; Yang B.; Huang T.; Jin X.-L.; Liu Q. Org. Lett.2024, 26, 1683.
(j) Qin W.; Ni Q.; Jiao W.; Ma Y. Chem. Commun.2023, 59, 7951.
(k) Hu L.; Li J.; Zhang Y.; Feng X.; Liu X. Chem. Sci.2022, 13, 4103.
[16](a) Ni Z.; Wang S.; Mao H.; Pan Y. Tetrahedron Lett.2012, 53, 3907.
(b) Xu H.; Gu S.; Chen W.; Li D.; Dou, J. J. Org. Chem.2011, 76, 2448.
(c) Kang X.; Lai S.; Liang X.; Zeng Q. Synthesis2022, 54, 3719.
[17](a) Li Z.; Liu G.; Huang, Z. J. Org. Chem.2025, 90, 11390.
(b) Siddiki S. M. A. H.; Touchy A. S.; Kon K.; Shimizu, K.-i. Chem. - Eur. J.2016, 22, 6111.
Options
Outlines

/

〈 〉