Sulfonyl fluorides (R‑SO2F) have emerged as versatile building blocks in organic synthesis, medicinal chemistry, and materials science, owing to their excellent stability and unique reactivity. Herein, we report a concise copper-catalyzed protocol for the synthesis of carbonyl-containing aliphatic sulfonyl fluorides from unstrained cycloalkyl silyl peroxides, involving sequential ring-opening, SO₂ insertion, and fluorination of alkyl radicals. This approach features mild conditions, operational simplicity, and broad substrate scope, tolerating various cyclic skeletons and functional groups. Furthermore, the products readily undergo diverse downstream SuFEx derivatizations, providing a new strategy for the assembly of structurally diverse alkyl sulfonyl fluorides.
Ma Yuxue
,
Pei Niping
,
Li Yanhui
,
Li Wei
,
Wang Lijing
. Copper-Catalyzed Ring-Opening Fluorosulfonylation of Unstrained cyclic Alkylsilyl Peroxides[J]. Chinese Journal of Organic Chemistry, 0
: 202604016
.
DOI: 10.6023/cjoc202604016
[1] Dong J.; Krasnova L.; Finn M.G.; Sharpless,K B. Angew. Chem. Int. Ed. Engl. 2014, 53(36): 9430-9448.
[2] Dubiella, C. Cui, H. Gersch; M. Brouwer, A. J.; Sieber, S. A; Kruger, A.; Liskamp, R. M.; Groll, M. Angew. Chem. Int. Ed. Engl. 2014, 53(44): 11969-73.
[3] Chen W; Dong J; Plate L; Mortenson D. E; Brighty G. J; Li S; Liu Y; Galmozzi A; Lee P. S; Hulce J. J; Cravatt B. F; Saez E; Powers E. T.Wilson; I. A; Sharpless, K. B; Kelly, J. W. [J]. Am. Chem. Soc. 2016, 138(23): 7353-64.
[4] Gu C; Shannon D. A; Colby T; Wang Z; Shabab M; Kumari S; Villamor, Joji. g; Mclaughlin Christopher, j; Weerapana, E; Kaiser, M; Cravatt Benjamin, f; Van der hoorn Renier, a. L. Chemistry. Biology. 2013, 20(4): 541-548.
[5] Cheng Y; Gu C; Han J; Chen Y; Tian Y; Zhu C; Xie J. Nature.Catalysis. 2026, 9(1): 18-27.
[6] Xu Y; Wang J; Zhang Q; Hu X; Lv C; Yang H; Sun B; Jin C. Angew. Chem. Int. Ed.Engl. 2025, 64(19): e202500561.
[7] Giel M. C; Smedley C. J; Mackie E. R.R; Guo, T; Dong, J; Soares Da Costa, T. P; Moses, J. E. Angew. Chem. Int. Ed. Engl. 2020, 59(3): 1181-1186.
[8] Wang N; Yang B; Fu C; Zhu H; Zheng F; Kobayashi T; Liu J; Li S; Ma C; Wang P. G; Wang Q; Wang L. J. Am. Chem. Soc. 2018, 140(15): 4995-4999.
[9] Martin-Gago, P; Olsen, C. A. Angew. Chem. Int. Ed. Engl. 2019, 58(4): 957-966.
[10] Liu F; Wang H; Li S; Bare, G. a. L; Chen, X; Wang, C; Moses, J. E; Wu, P; Sharpless, K. B. Angew. Chem. Int. Ed. Engl. 2019, 58(24): 8029-8033.
[11] Meng G; Guo T; Ma T; Zhang J; Shen Y; Sharpless K. B; Dong J. Nature. 2019, 574(7776): 86-89.
[12] Bai M; Liu S; Xin H; Yang X; Duan X. H; Guo L. N. Org. Biomol. Chem. 2023, 21(28): 5855-5860.
[13] Li T. T; Cheng Y; Xiao W. J; Shi D. Q; Chen J. R. Chem. Cat. Chem. 2023, 15(23):8955-8958.
[14] Liu S; Zhang L; Xu L; Gao P; Duan X. H; Guo L. N. Org. Lett. 2023, 25(8): 1336-1341.
[15] Ma Z; Liu Y; Ma X; Hu X; Guo Y; Chen Q-Y; Liu C. Organic. Chemistry. Frontiers. 2022, 9(4): 1115-1120.
[16] Zhang H; Li S; Zheng H-L; Zhu G; Liao S; Nie X. Organic. Chemistry. Frontiers. 2022, 9(18): 4854-4860.
[17] Chen Z. D; Zhou X; Yi J. T; Diao H. J; Chen Q. L; Lu G; Weng J. Org.Lett. 2022, 24(13): 2474-2478.
[18] Nguyen V. T; Haug G. C; Nguyen V. D; Vuong N. T.H; Karki, G. B; Arman, H. D; Larionov, O. V. Chem. Sci. 2022, 13(14): 4170-4179.
[19] Vincent C. A; Chiriac M. I; Troian-Gautier, L; Tambar, U. K. ACS. Catal. 2023, 13(6): 3668-3675.
[20] Sarver P. J; Bissonnette N. B; Macmillan D. W.C. [J]. Am. Chem. Soc. 2021, 143(26): 9737-9743.
[21] Jin S; Haug G. C; Trevino R; Nguyen V. D; Arman H. D; Larionov O. V. Chem. Sci. 2021, 12(41): 13914-13921.
[22] Qu S; Li X-X; Li X; Wang L. ACS.Catalysis. 2024, 14(5): 4318-4328.
[23] Zhang H; Sun X; Ma C; Li C; Ni Y; Yu Y; Xu Y-Q; Ni S-F; Cao Z-Y. ACS. Catalysis. 2024, 14(5): 3115-3127.
[24] Shan Q. C; Liu S; Shen Y; Ma M; Duan X. H; Gao P; Guo L. N.Org Lett. 2022, 24(36): 6653-6657.
[25] Zhong W; Xu W; Yang Q; Kato T; Liu Y; Maruoka K.Tetrahedron. 2022, 112.
[26] Liu S; Bai M; Xu P. F; Sun Q. X; Duan X. H; Guo L. N. Chem. Commun. Camb. 2021, 57(69): 8652-8655.
[27] Sun Q. X; Chen H; Liu S; Wang X. Q; Duan X. H; Guo L. N.[J]. Org. Chem. 2021, 86(17): 11987-11997.
[28] Xin H; Yuan Z. H; Yang M; Wang M. H; Duan X. H; Guo L. N. Green. Chemistry. 2021, 23(23): 9549-9553.
[29] Zhang T. Y; Wu Y; Liu S; Tao J. Q; Yang X; Wang X. Q; Duan X. H; Guo L. N. Org. Lett. 2023, 25(23): 4329-4334.
[30] Sakamoto R; Kato T; Sakurai S; Maruoka K. Org.Lett. 2018, 20(5): 1400-1403.
[31] Sakurai S; Kano T; Maruoka K.Chem. Commun. Camb. 2021, 57(1): 81-84.
[32] Xu W; Liu Y; Kato T; Maruoka K. Org.Lett. 2021, 23(5): 1809-1813.
[33] Yan Z. M; Qi L; Du H. J; Zhao Z. Q; Liu J. L; Dong Y. C; Li W; Wang L. J. Org. Lett. 2023, 25(38): 7051-7056.
[34] An Z; Miao M; Sun F; Lan X. B; Yu J. Q; Guo X; Zhang J. Org. Biomol. Chem. 2024, 22(12): 2370-2374.
[35] Nagano S; Maeda N; Kato T; Matsumoto A; Maruoka K.Tetrahedron.Letters. 2023, 122.
[36] Liu C; Wang J; Liu X; Feng J; Du D. Chem.Commun. 2023, 59(88): 13175-13178.
[37] Ma Y. J; Yuan Z. H; Gao P; Duan X. H; Xin H; Liu L; Guo L. N.[J]. Org. Chem. 2023, 88(14): 9927-9940.
[38] Ying Y; Ye Z; Wang A; Chen X; Meng S; Xu P; Gao Y; Zhao Y. Org.Lett. 2023, 25(6): 928-932.