A new method for selective cleavage of sulfonimides into sulfonamides in high yields using a simple electrochemical approach is shown. As revealed by the electrochemical study, the aromatic sulfonimides can be selectively cleaved by electrolysis of the starting compound at a given potential (only -0.9 V vs SCE for the nosyl group). The high chemoselectivity was confirmed by preparative electrolysis, and the results were supported with DFT calculations of a set of substances bearing different sulfonimide functions. Moreover, various experimental setups together with other attempts to simplify the procedure were tested. Finally, the removal of the p-nosyl group from the corresponding sulfonimides proceeds smoothly regardless of the number of nosyl groups and the overall shape of the complex molecule. Thus, the method is interesting for use in the field of multifunctional molecules such as calix[n]arenes.

Department of Organic Chemistry UCTP Technická 5 166 28 Prague 6 Czech Republic

Department of Physical Chemistry University of Chemistry and Technology Prague Technická 5 166 28 Prague 6 Czech Republic

Institute of Chemical Process Fundamentals of Czech Academy of Sciences v v i Rozvojová 135 165 02 Prague 6 Czech Republic

J Heyrovský Institute of Physical Chemistry of Czech Academy of Sciences v v i Dolejškova 2155 3 182 23 Prague 8 Czech Republic

Zobrazit více v PubMed

Apaydın S.; Török M. Sulfonamide derivatives as multi-target agents for complex diseases. Bioorg. Med. Chem. Lett. 2019, 29 (16), 2042–2050. 10.1016/j.bmcl.2019.06.041. PubMed DOI

Mondal S.; Malakar S. Synthesis of sulfonamide and their synthetic and therapeutic applications: Recent advances. Tetrahedron 2020, 76 (48), 131662.10.1016/j.tet.2020.131662. DOI

Ovung A.; Bhattacharyya J. Sulfonamide drugs: structure, antibacterial property, toxicity, and biophysical interactions. Biophys. Rev. 2021, 13 (2), 259–272. 10.1007/s12551-021-00795-9. PubMed DOI PMC

Chan M.; Lao F. S.; Chu P. J.; Shpigelman J.; Yao S.; Nan J.; Sato-Kaneko F.; Li V.; Hayashi T.; Corr M.; Carson D. A.; Cottam H. B.; Shukla N. M. Structure-Activity Relationship Studies To Identify Affinity Probes in Bis-aryl Sulfonamides That Prolong Immune Stimuli. J. Med. Chem. 2019, 62 (21), 9521–9540. 10.1021/acs.jmedchem.9b00870. PubMed DOI PMC

Chen L.; Berry S. N.; Wu X.; Howe E. N. W.; Gale P. A. Advances in Anion Receptor Chemistry. Chem 2020, 6 (1), 61–141. 10.1016/j.chempr.2019.12.002. DOI

Pal S.; Ghosh T. K.; Ghosh R.; Mondal S.; Ghosh P. Recent advances in recognition, sensing and extraction of phosphates: 2015 onwards. Coord. Chem. Rev. 2020, 405, 213128.10.1016/j.ccr.2019.213128. DOI

Manna U.; Das G. An overview of anion coordination by hydroxyl, amine and amide based rigid and symmetric neutral dipodal receptors. Coord. Chem. Rev. 2021, 427, 213547.10.1016/j.ccr.2020.213547. DOI

Batool M.; Afzal Z.; Junaid H. M.; Solangi A. R.; Hassan A. Sulfonamides as Optical Chemosensors. Crit. Rev. Anal. Chem. 2022, 1–28. 10.1080/10408347.2022.2105135. PubMed DOI

Lukin O.; Gramlich V.; Kandre R.; Zhun I.; Felder T.; Schalley C. A.; Dolgonos G. Designer Dendrimers: Branched Oligosulfonimides with Controllable Molecular Architectures. J. Am. Chem. Soc. 2006, 128 (27), 8964–8974. 10.1021/ja061606b. PubMed DOI

Lukin O.; Schubert D.; Müller C.; Corda M.; Kandre R. Persulfonylation of Amines Applied to the Synthesis of Higher Generation Dendrimers. J. Org. Chem. 2008, 73 (9), 3562–3565. 10.1021/jo800179m. PubMed DOI

Schubert D.; Corda M.; Lukin O.; Brusilowskij B.; Fiškin E.; Schalley C. A. A Topological View of Isomeric Dendrimers. Eur. J. Org Chem. 2008, 2008 (24), 4148–4156. 10.1002/ejoc.200800408. DOI

Bondareva J.; Rozhkov V.; Kachala V. V.; Fetyukhin V.; Lukin O. An optimized divergent synthesis of sulfonimide-based dendrimers achieving the fifth generation. Synth. Commun. 2019, 49 (24), 3536–3545. 10.1080/00397911.2019.1676909. DOI

Bondareva J.; Kolotylo M.; Rozhkov V.; Burilov V.; Lukin O. A convergent approach to sulfonimide-based dendrimers and dendrons. Tetrahedron Lett. 2020, 61 (25), 152011.10.1016/j.tetlet.2020.152011. DOI

Mondal S. Sulfonamide synthesis under green conditions. Synth. Commun. 2021, 51 (7), 1023–1044. 10.1080/00397911.2020.1870238. DOI

Kim D. H.; Yun B. H.; Choi E. W.; Oh S. M.; Alam M.; Lee K. T.; Lee Y. S. Synthesis and Cytotoxic Effects of Sulfonamide-Substituted 5,6,7-Trimethoxyflavones on Human Cancer Cell Lines. Bull. Korean Chem. Soc. 2013, 34 (8), 2507–2510. 10.5012/bkcs.2013.34.8.2507. DOI

Yasuhara A.; Kameda M.; Sakamoto T. Selective Monodesulfonylation of N, N-Disulfonylarylamines with Tetrabutylammonium Fluoride. Chem. Pharm. Bull. 1999, 47 (6), 809–812. 10.1248/cpb.47.809. DOI

Torti E.; Protti S.; Merli D.; Dondi D.; Fagnoni M. Photochemistry of N-Arylsulfonimides: An Easily Available Class of Nonionic Photoacid Generators (PAGs). Chem.—Eur. J. 2016, 22 (47), 16998–17005. 10.1002/chem.201603522. PubMed DOI

Klein M.; König B. Synthesis and thermal cyclization of an enediyne-sulfonamide. Tetrahedron 2004, 60 (5), 1087–1092. 10.1016/j.tet.2003.11.078. DOI

Senboku H.; Nakahara K.; Fukuhara T.; Hara S. Hg cathode-free electrochemical detosylation of N,N-disubstituted p-toluenesulfonamides: mild, efficient, and selective removal of N-tosyl group. Tetrahedron Lett. 2010, 51 (2), 435–438. 10.1016/j.tetlet.2009.11.056. DOI

Viaud P.; Coeffard V.; Thobie-Gautier C.; Beaudet I.; Galland N.; Quintard J.-P.; Le Grognec E. Electrochemical Cleavage of Sulfonamides: An Efficient and Tunable Strategy to Prevent β-Fragmentation and Epimerization. Org. Lett. 2012, 14 (3), 942–945. 10.1021/ol300003f. PubMed DOI

Kossai R.; Jeminet G.; Simonet J. Cathodic behaviour of p-toluenesulfonamides in organic solvents. Electrochim. Acta 1977, 22 (12), 1395–1402. 10.1016/0013-4686(77)85150-5. DOI

Liška A.; Řezanková M.; Klíma J.; Urban J.; Budka J.; Ludvík J. Electrochemical, EPR, and quantum chemical study of reductive cleavage of cone-Calix [4] arene nosylates-New electrosynthetic approach. Electrochem. Sci. Adv. 2022, 3, e210022110.1002/elsa.202100221. DOI

Civitello E. R.; Rapoport H. The regioselective cleavage of aryl tosylates by electrochemical reduction. J. Org. Chem. 1992, 57 (3), 834–840. 10.1021/jo00029a010. DOI

Huang B.; Guo L.; Xia W. A facile and versatile electro-reductive system for hydrodefunctionalization under ambient conditions. Green Chem. 2021, 23 (5), 2095–2103. 10.1039/D1GC00317H. DOI

Maia H. L. S.; Medeiros M. J.; Montenegro M. I.; Court D.; Pletcher D. Deprotection by electrolysis: Part I. The application of homogeneous redox catalysis to the study of the reduction of tosyl esters and amides. J. Electroanal. Chem. Interfacial Electrochem. 1984, 164 (2), 347–361. 10.1016/S0022-0728(84)80217-X. DOI

Fry A. J.The Electrochemistry of Nitro, Nitroso, and Related Compounds. In PATAI’S Chemistry of Functional Groups; Wiley, 1996; pp 837–856.

Squella J. A.; Bollo S.; Nunez-Vergara L. Recent Developments in the Electrochemistry of Some Nitro Compounds of Biological Significance. Curr. Org. Chem. 2005, 9, 565–581. 10.2174/1385272053544380. DOI

Huang L.-Z.; Hansen H. C. B.; Bjerrum M. J. Electrochemical reduction of nitroaromatic compounds by single sheet iron oxide coated electrodes. J. Hazard. Mater. 2016, 306, 175–183. 10.1016/j.jhazmat.2015.12.009. PubMed DOI

Salvadori K.; Ludvík J.; Šimková L.; Matějka P.; Cuřínová P. Nitro group as a redox switch in urea-based receptors of anions. J. Electroanal. Chem. 2021, 902, 115816.10.1016/j.jelechem.2021.115816. DOI

Brillas E.; Farnia G.; Severin M.; Vianello E. Self-protonation effects in the electrochemical reduction mechanism of p-nitrobenzoic acid. Electrochim. Acta 1986, 31 (7), 759–766. 10.1016/0013-4686(86)85004-6. DOI

Asirvatham M. R.; Hawley M. D. Electrochemical studies of the formation and decomposition of p-nitrobenzenesulfonamide radical anions. J. Electroanal. Chem. Interfacial Electrochem. 1974, 53 (2), 293–305. 10.1016/S0022-0728(74)80142-7. DOI

Saji T.; Ito N. The Electrochemical Cleavage of Carbon-Halogen Bonds of Haloferrocenes. Bull. Chem. Soc. Jpn. 1985, 58, 3375–3376. 10.1246/bcsj.58.3375. DOI

Luca O. R.; Gustafson J. L.; Maddox S. M.; Fenwick A. Q.; Smith D. C. Catalysis by electrons and holes: formal potential scales and preparative organic electrochemistry. Org. Chem. Front. 2015, 2 (7), 823–848. 10.1039/C5QO00075K. DOI

Elgrishi N.; Rountree K. J.; McCarthy B. D.; Rountree E. S.; Eisenhart T. T.; Dempsey J. L. A Practical Beginner’s Guide to Cyclic Voltammetry. J. Chem. Educ. 2018, 95 (2), 197–206. 10.1021/acs.jchemed.7b00361. DOI

Gutsche C. D.Calixarenes Revisited; The Royal Society of Chemistry: Thomas, Graham House, Cambridge, 1998.

Gutsche C. D.; Chemistry R. S. o.. Calixarenes: An Introduction; The Royal Society of Chemistry: Thomas, Graham House, Cambridge, 2008.

Mandolini L.; Ungaro R.. Calixarenes in Action; World Scientific Publishing Company, 2000.

Vicens J.; Harrowfield J.; Baklouti L.. Calixarenes in the Nanoworld; Springer: Dordrecht, 2007.

Li H.; Jiang H.; Liu C.; Zhu C.; Zhu X. P. Electrochemical Oxidation of Sulfonamides with Boron-Doped Diamond and Pt Anodes. ChemistryOpen 2019, 8 (12), 1421–1428. 10.1002/open.201900250. PubMed DOI PMC

Salvadori K.; Šimková L.; Císařová I.; Sýkora J.; Ludvík J.; Cuřínová P. Sulphonamidic Groups as Electron-Withdrawing Units in Ureido-Based Anion Receptors: Enhanced Anion Complexation versus Deprotonation. ChemPlusChem 2020, 85 (7), 1401–1411. 10.1002/cplu.202000326. PubMed DOI

Chen L.; Lang H.; Fang L.; Zhu M.; Liu J.; Yu J.; Wang L. Nickel-Catalyzed One-Pot Suzuki-Miyaura Cross-Coupling of Phenols and Arylboronic Acids Mediated by N,N-Ditosylaniline. Eur. J. Org Chem. 2014, 2014 (23), 4953–4957. 10.1002/ejoc.201402475. DOI

Chen L.; Lang H.; Fang L.; Yu J.; Wang L. Nickel-Catalyzed Desulfitative Suzuki-Miyaura Cross-Coupling of N,N-Disulfonylmethylamines and Arylboronic Acids. Eur. J. Org Chem. 2014, 2014 (29), 6385–6389. 10.1002/ejoc.201402919. DOI

Debnath S.; Mondal S. Synthesis of a Series of 2-Aminodiarylsulfones by Brønsted Acid Mediated Regioselective Fries Type Rearrangement of N-Alkyl-N -arylbenzenesulfonamides. ChemistrySelect 2018, 3 (15), 4129–4132. 10.1002/slct.201800435. DOI

Pan C.; Cheng J.; Wu H.; Ding J.; Liu M. Cu(OAc)2-Catalyzed N-Arylation of Sulfonamides with Arylboronic Acids or Trimethoxy(phenyl)silane. Synth. Commun. 2009, 39 (12), 2082–2092. 10.1080/00397910802638495. DOI

Kato T.; Okamoto I.; Tanatani A.; Hatano T.; Uchiyama M.; Kagechika H.; Masu H.; Katagiri K.; Tominaga M.; Yamaguchi K.; Azumaya I. Spontaneous Resolution of Aromatic Sulfonamides: Effective Screening Method and Discrimination of Absolute Structure. Org. Lett. 2006, 8 (22), 5017–5020. 10.1021/ol061731s. PubMed DOI

Frisch M. J.; Trucks G. W.; Schlegel H. B.; Scuseria G. E.; Robb M. A.; Cheeseman J. R.; Scalmani G.; Barone V.; Petersson G. A.; Nakatsuji H.; Li X.; Caricato M.; Marenich A. V.; Bloino J.; Janesko B. G.; Gomperts R.; Mennucci B.; Hratchian H. P.; Ortiz J. V.; Izmaylov A. F.; Sonnenberg J. L.; Williams-Young D.; Ding F.; Lipparini F.; Egidi F.; Goings J.; Peng B.; Petrone A.; Henderson T.; Ranasinghe D.; Zakrzewski V. G.; Gao J.; Rega N.; Zheng G.; Liang W.; Hada M.; Ehara M.; Toyota K.; Fukuda R.; Hasegawa J.; Ishida M.; Nakajima T.; Honda Y.; Kitao O.; Nakai H.; Vreven T.; Throssell K.; Montgomery J. A. Jr.; Peralta J. E.; Ogliaro F.; Bearpark M. J.; Heyd J. J.; Brothers E. N.; Kudin K. N.; Staroverov V. N.; Keith T. A.; Kobayashi R.; Normand J.; Raghavachari K.; Rendell A. P.; Burant J. C.; Iyengar S. S.; Tomasi J.; Cossi M.; Millam J. M.; Klene M.; Adamo C.; Cammi R.; Ochterski J. W.; Martin R. L.; Morokuma K.; Farkas O.; Foresman J. B.; Fox D. J.. Gaussian 16 Rev. C.01; Gaussian, Inc.: Wallingford, CT, 2016.