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DOI: 10.1055/a-2545-7313
Alkylation of Arylsulfonyl Cyanides To Form Alkyl Sulfones
This research was supported in part by the US Department of Defense/National Defense Education Program through the Educational and Research Training Collaborative at UIC, award HQ 00342010037. Partial support was also provided by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Grant DE-SC0021055 to N.P.M.
Abstract
Arylsulfonyl cyanides, such as commercially available TsCN, undergo base-mediated C–S coupling with alkyl halides to provide alkyl sulfones. A wide range of alkyl halides with diverse functionalities were found to react with moderate to high efficiency. Based on experimental observations, it is proposed that the arylsulfonyl cyanides react with the base to in situ generate arylsulfinates, which then act as SN2 nucleophiles towards the alkyl halides. A major advantage of this method is that it circumvents the problem of metal sulfinate nucleophiles having low solubility, by using soluble arylsulfonyl cyanides as soluble pro-nucleophiles.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2545-7313.
- Supporting Information
Publication History
Received: 07 January 2025
Accepted after revision: 25 February 2025
Accepted Manuscript online:
25 February 2025
Article published online:
20 March 2025
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References and Notes
- 1 Current address: Department of Chemistry, Princeton University, Princeton, NJ 08544, USA
- 2 Tilby MJ, Willis MC. Expert Opin. Drug Discov. 2021; 16: 1227
- 3a Hughes JM. E, Fier PS. Org. Lett. 2019; 21: 5650
- 3b Merchant RR, Edwards JT, Qin T, Kruszyk MM, Bi C, Che G, Bao D.-H, Qiao W, Sun L, Collins MR, Fadeyi OO, Gallego GM, Mousseau JJ, Nuhant P, Baran PS. Science 2018; 360: 75
- 4 Ariki ZT, Maekawa Y, Nambo M, Crudden CM. J. Am. Chem. Soc. 2018; 140: 78
- 5 Huang M, Tang M, Hu J, Westcott SA, Radius U, Marder TB. Chem. Commun. 2022; 58: 395
- 6 Liang S, Hofman K, Friedrich M, Keller J, Manolikakes G. ChemSusChem 2021; 14: 4878
- 7 Liu N.-W, Liang S, Manolikakes G. Synthesis 2016; 48: 1939
- 8 Liu J, Zheng L. Adv. Synth. Catal. 2019; 361: 1710
- 9 Zhu J, Yang W, Wang X, Wu L. Adv. Synth. Catal. 2018; 360: 386
- 10 Deeming AS, Emmett EJ, Richards-Taylor CS, Willis MC. Synthesis 2014; 46: 2701
- 11 Emmett EJ, Willis MC. Asian. J. Org. Chem. 2015; 4: 602
- 12 Kowalski P, Mitka K, Ossowska K, Kolarska Z. Tetrahedron 2005; 61: 1933
- 13 Kaczorowska K, Kolarska Z, Mitka K, Kowalski P. Tetrahedron 2005; 61: 8315
- 14 Reddy LR, Hu B, Prashad M, Prasad K. Angew. Chem. Int. Ed. 2009; 48: 172
- 15 Wang F, Rao W, Wang S.-Y. J. Org. Chem. 2021; 86: 8970
- 16 Liu Y, Li R, Yu B. Org. Biomol. Chem. 2024; 22: 196
- 17 Huang A.-X, Li R, Lv Q.-Y, Yu B. Chem. Eur. J. 2024; 30: e202402416
- 18 Akula R, Xiong Y, Ibrahim H. RSC Adv. 2013; 3: 10731
- 19 Barton DH. R, Jaszberenyi JCs, Theodorakis EA. Tetrahedron 1991; 47: 9167
- 20 Shyam PK, Jang H.-Y. J. Org. Chem. 2017; 82: 1761
- 21 Johnson MW, Bagley SW, Mankad NP, Bergman RG, Mascitti V, Toste FD. Angew. Chem. Int. Ed. 2014; 53: 4404
- 22 Roy T, Lee J.-W. Synlett 2020; 31: 455
- 23 Borys AM. Organometallics 2023; 42: 182
- 24 Pangborn AB, Giardello MA, Grubbs RH, Rosen RK, Timmers FJ. Organometallics 1996; 15: 1518
- 25 Song Y, Li C, Hu X, Zhang H, Mao Y, Wang X, Wang C, Hu L, Yan J. Green Chem. 2024; 26: 6578
- 26 De Vos D, Cunha AV, Jei BB, Maes BU. W. ACS Catal. 2024; 14: 12282
- 27 Payra S, Yadav N, Moorthy JN. New J. Chem. 2022; 46: 582
- 28 Meng Y, Wang M, Jiang X. Angew. Chem. Int. Ed. 2020; 59: 1346
- 29 Takano H, You Y, Hayashi H, Harabuchi Y, Maeda S, Mita T. ACS Omega 2021; 6: 33846
- 30 He J, Chen G, Zhang B, Li Y, Chen J.-R, Xiao W.-J, Liu F, Li C. Chem 2020; 6: 1149
- 31 Ozaki T, Yorimitsu H, Perry GJ. P. Chem. Eur. J. 2021; 27: 15387
- 32 Yang Y.-Z, Li Y, Lv G.-F, He D.-L, Li J.-H. Org. Lett. 2022; 24: 5115
- 33 Srinivas BT. V, Rawat VS, Konda K, Sreedhar B. Adv. Synth. Catal. 2014; 356: 805