Abstract
An effective approach toward conversion of phenols to their benzene sulfonate esters by using N-fluorobenzenesufonimide (NFSI) and catalytic potassium fluoride is demonstrated. Mild reaction conditions, shorter reaction time, excellent yield and easy-to-handle reagents are the key features of the methodology. Mild reaction conditions have conferred wide substrate tolerability and sensitive substrates are well preserved during the reaction. Sulfonate ester formation is governed by benzenesulfonyl fluoride which is in situ generated after addition of KF to NFSI and KF is regenerated after sulfonylation when potassium carbonate is used as a base.
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References
Alam MS, Koo S (2018) Deprotection of durable benzenesulfonyl protection for phenols — efficient synthesis of polyphenols. Synth Commun 48(3):247–254. https://doi.org/10.1080/00397911.2017.1393088
Ali AM, Hill B, Taylor SD (2009) Trichloroethyl group as a protecting group for sulfonates and its application to the synthesis of a disulfonate analog of the tyrosine sulfated PSGL-1 43–50 peptide. J Org Chem 74(9):3583–3586. https://doi.org/10.1021/jo900122c
Aziz J, Messaoudi S, Alami M, Hamze A (2014) Sulfinate derivatives: dual and versatile partners in organic synthesis. Org Biomol Chem 12(48):9743–9759. https://doi.org/10.1039/C4OB01727G
Bouchez LC, Dubbaka SR, Turks M, Vogel P (2004) Sulfur dioxide mediated one-pot, three-and four-component syntheses of polyfunctional sulfonamides and sulfonic esters: study of the stereoselectivity of the ene reaction of sulfur dioxide. J Org Chem 69(19):6413–6418
Cai C, Rivera NR, Balsells J, Sidler RR, McWilliams JC, Shultz CS, Sun Y (2006) An efficient catalyst for Pd-catalyzed carbonylation of aryl arenesulfonates. Org Lett 8(22):5161–5164. https://doi.org/10.1021/ol062208g
Cho C-H, Yun H-S, Park K (2003) Nickel(0)-catalyzed cross-coupling of alkyl arenesulfonates with aryl grignard reagents. J Org Chem 68(8):3017–3025. https://doi.org/10.1021/jo026449n
Choi JH, Lee BC, Lee HW, Lee I (2002) Competitive reaction pathways in the nucleophilic substitution reactions of aryl benzenesulfonates with benzylamines in acetonitrile. J Org Chem 67(4):1277–1281. https://doi.org/10.1021/jo0161835
Deeming AS, Russell CJ, Hennessy AJ, Willis MC (2014) DABSO-based, three-component, one-pot sulfone synthesis. Org Lett 16(1):150–153
Dond BD, Thore SN (2020) NFSI/KF mediated mild and chemoselective interconversion of aryl TBDMS ethers to their benzene sulfonate. Tetrahedron Lett 61(13):151660. https://doi.org/10.1016/j.tetlet.2020.151660
Duarte F, Geng T, Marloie G, Al Hussain AO, Williams NH, Kamerlin SCL (2014) The alkaline hydrolysis of sulfonate esters: challenges in interpreting experimental and theoretical data. J Org Chem 79(7):2816–2828. https://doi.org/10.1021/jo402420t
Elder DP, Delaney E, Teasdale A, Eyley S, Reif VD, Jacq K, Facchine KL, Oestrich RS, Sandra P, David F (2010) The utility of sulfonate salts in drug development. J Pharm Sci 99(7):2948–2961. https://doi.org/10.1002/jps.22058
Feng M, Tang B, HLiang S, Jiang X (2016) Sulfur containing scaffolds in drugs: synthesis and application in medicinal chemistry. CTMC 16(11):1200–1216. https://doi.org/10.2174/1568026615666150915111741
Gao J, Pan X, Liu J, Lai J, Chang L, Yuan G (2015) Iodine-induced synthesis of sulfonate esters from sodium sulfinates and phenols under mild conditions. RSC Adv 5(35):27439–27442. https://doi.org/10.1039/C5RA00724K
Gembus V, Marsais F, Levacher V (2008) An efficient organocatalyzed interconversion of silyl ethers to tosylates using DBU and p-toluenesulfonyl fluoride. Synlett 2008(10):1463–1466. https://doi.org/10.1055/s-2008-1078407
Giang Luu T, Tan Bui T, Kim H-K (2022) Visible-light-induced one-pot synthesis of sulfonic esters via multicomponent reaction of arylazo sulfones and alcohols. RSC Adv 12(27):17499–17504. https://doi.org/10.1039/D2RA02656B
Gooßen LJ, Rodríguez N, Lange PP, Linder C (2010) Decarboxylative cross-coupling of aryl tosylates with aromatic carboxylate salts. Angew Chem Int Ed 49(6):1111–1114. https://doi.org/10.1002/anie.200905953
Hansch C, Sammes PG, Peter G, Taylor JB, John B (1990) Comprehensive medicinal chemistry : the rational design, mechanistic study and therapeutic application of chemical compounds. Pergamon, Oxford
Khashi M, Davoodnia A, Chamani J (2014) Dmap-catalyzed synthesis of novel pyrrolo[2,3-D]pyrimidine derivatives bearing an aromatic sulfonamide moiety. Phosphorus Sulfur Silicon Relat Elem 189(6):839–848. https://doi.org/10.1080/10426507.2013.858253
Li H-S, Liu G (2014) Copper/silver-mediated cascade reactions for the construction of 2-sulfonylbenzo[b ]furans from trans -2-hydroxycinnamic acids and sodium sulfinates. J Org Chem 79(2):509–516. https://doi.org/10.1021/jo4024478
Li X, Xu Y, Wu W, Jiang C, Qi C, Jiang H (2014) Copper-catalyzed aerobic oxidative ns bond functionalization for cs bond formation: regio- and stereoselective synthesis of sulfones and thioethers. Chem Eur J 20(26):7911–7915. https://doi.org/10.1002/chem.201402815
Liu N-W, Liang S, Manolikakes G (2016) Recent advances in the synthesis of sulfones. Synthesis 48(13):1939–1973. https://doi.org/10.1055/s-0035-1560444
Marković D, Volla CM, Vogel P, Varela-Álvarez A, Sordo JA (2010) BCl3-mediated ene reaction of sulfur dioxide and unfunctionalized alkenes. Chem A Eur J 16(20):5969–5975
Martinelli MJ, Vaidyanathan R, Pawlak JM, Nayyar NK, Dhokte UP, Doecke CW, Zollars LMH, Moher ED, Khau VV, Košmrlj B (2002) Catalytic regioselective sulfonylation of α-chelatable alcohols: scope and mechanistic insight. J Am Chem Soc 124(14):3578–3585. https://doi.org/10.1021/ja016031r
Movassagh B, Shokri S (2005) An efficient one-pot conversion of THP- and TMS ethers to sulfonate esters using FeCl3-montmorillonite K-10 clay. Zeitschrift Für Naturforschung B 60(7):763–765. https://doi.org/10.1515/znb-2005-0711
Nguyen HN, Huang X, Buchwald SL (2003) The first general palladium catalyst for the suzuki−miyaura and carbonyl enolate coupling of aryl arenesulfonates. J Am Chem Soc 125(39):11818–11819. https://doi.org/10.1021/ja036947t
Rezaei N, Movassagh B (2016) Polystyrene resin-supported CuI-cryptand 22 complex: a highly efficient and reusable catalyst for the formation of aryl–sulfur bonds in aqueous media. Tetrahedron Lett 57(14):1625–1628. https://doi.org/10.1016/j.tetlet.2016.03.005
Ryckebusch A, Déprez-Poulain R, Debreu-Fontaine M-A, Vandaele R, Mouray E, Grellier P, Sergheraert C (2002) Parallel synthesis and anti-malarial activity of a sulfonamide library. Bioorg Med Chem Lett 12(18):2595–2598. https://doi.org/10.1016/S0960-894X(02)00475-4
Scott KA, Njardarson JT (2019) Analysis of US FDA-Approved Drugs Containing Sulfur Atoms. In: Jiang X (ed) Sulfur Chemistry. Springer International Publishing, Cham, pp 1–34
Simpkins NS, Baldwin JE (2013) Sulphones in Organic Synthesis. Elsevier Science, Kent
Singh A, Yi H, Zhang G, Bian C, Pei P, Lei A (2017) Photoinduced oxidative cross-coupling for O–S bond formation: a facile synthesis of alkyl benzenesulfonates. Synlett 28(13):1558–1563. https://doi.org/10.1055/s-0036-1588728
Stang PJ (1991) Alkynyl carboxylate, phosphate, and sulfonate esters. Acc Chem Res 24(10):304–310. https://doi.org/10.1021/ar00010a004
Tang Z-Y, Hu Q-S (2004) Room-temperature Ni(0)-catalyzed cross-coupling reactions of aryl arenesulfonates with arylboronic acids. J Am Chem Soc 126(10):3058–3059. https://doi.org/10.1021/ja038752r
Toogood PL, Harvey PJ, Repine JT, Sheehan DJ, VanderWel SN, Zhou H, Keller PR, McNamara DJ, Sherry D, Zhu T, Brodfuehrer J, Choi C, Barvian MR, Fry DW (2005) Discovery of a potent and selective inhibitor of cyclin-dependent kinase 4/6. J Med Chem 48(7):2388–2406. https://doi.org/10.1021/jm049354h
Wang P, Min J, Nwachukwu JC, Cavett V, Carlson KE, Guo P, Zhu M, Zheng Y, Dong C, Katzenellenbogen JA, Nettles KW, Zhou H-B (2012) Identification and structure-activity relationships of a novel series of estrogen receptor ligands based on 7-thiabicyclo [2.2.1]hept-2-ene-7-oxide. J Med Chem 55(5):2324–2341. https://doi.org/10.1021/jm201556r
Wei W, Liu C, Yang D, Wen J, You J, Suo Y, Wang H (2013) Copper-catalyzed direct oxysulfonylation of alkenes with dioxygen and sulfonylhydrazides leading to β-ketosulfones. Chem Commun 49(87):10239. https://doi.org/10.1039/c3cc45803b
Wilden JD, Geldeard L, Lee CC, Judd DB, Caddick S (2007) Trichlorophenol (TCP) sulfonate esters: a selective alternative to pentafluorophenol (PFP) esters and sulfonyl chlorides for the preparation of sulfonamides. Chem Commun 10:1074–1076. https://doi.org/10.1039/B614604J
Wu Z, Song H, Cui X, Pi C, Du W, Wu Y (2013) Sulfonylation of quinoline N -oxides with aryl sulfonyl chlorides via copper-catalyzed C-H bonds activation. Org Lett 15(6):1270–1273. https://doi.org/10.1021/ol400178k
Yeung PY, So CM, Lau CP, Kwong FY (2010) A mild and efficient palladium-catalyzed cyanation of aryl mesylates in water or tBuOH/water. Angew Chem 122(47):9102–9106. https://doi.org/10.1002/ange.201005121
Yoshino H, Ueda N, Niijima J, Sugumi H, Kotake Y, Koyanagi N, Yoshimatsu K, Asada M, Watanabe T, Nagasu T, Tsukahara K, Iijima A, Kitoh K (1992) Novel sulfonamides as potential, systemically active antitumor agents. J Med Chem 35(13):2496–2497. https://doi.org/10.1021/jm00091a018
Zhao X, Dimitrijević E, Dong VM (2009) Palladium-catalyzed C−H bond functionalization with arylsulfonyl chlorides. J Am Chem Soc 131(10):3466–3467. https://doi.org/10.1021/ja900200g
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Dond, B.D., Pansare, D.N., Sarkate, A.P. et al. A facile synthesis of sulfonate esters from phenols using catalytic KF/NFSI and K2CO3. Chem. Pap. 77, 1765–1772 (2023). https://doi.org/10.1007/s11696-022-02585-3
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DOI: https://doi.org/10.1007/s11696-022-02585-3