Synlett, Inhaltsverzeichnis Synlett 2021; 32(05): 488-490DOI: 10.1055/s-0040-1707109 cluster The Power of Transition Metals: An Unending Well-Spring of New Reactivity © Georg Thieme Verlag Stuttgart · New YorkFacile C–S Bond Cleavage of Aryl Sulfoxides Promoted by Brønsted Acid Authors ‡ Bogdan R. Brutiu Immo Klose Nuno Maulide ∗ Artikel empfehlen Abstract Artikel einzeln kaufen(opens in new window) Alle Artikel dieser Rubrik(opens in new window) Dedicated with respect and admiration to Prof. Barry M. Trost, a founding member of Science of Synthesis, on the occasion of the 20th anniversary of Science of Synthesis. ‡ These authors contributed equally to this work Abstract A method for the Brønsted acid promoted desulfination of aryl sulfoxides is presented. In the presence of a thiol, electron-rich sulfoxides undergo C–S bond cleavage to give the corresponding protodesulfinated arenes and disulfides. Key words Key wordssulfoxides - protodesulfination - deprotection - acid Volltext Referenzen References and Notes 1a Jia T, Wang M, Liao J. Top. Curr. Chem. 2019; 377: 1 1b Trost B, Rao M. Angew. Chem. Int. Ed. 2015; 54: 5026 1c Sipos G, Drinkel EE, Dorta R. Chem. Soc. Rev. 2015; 44: 3834 1d Otocka S, Kwiatkowska M, Madalińska L, Kiełbasiński P. Chem. Rev. 2017; 117: 4147 2a Frey J, Jerhaoui S, Choppin S, Wencel-Delord J, Colobert F. ACS Catal. 2018; 8: 2805 2b Aitken HR. M, Furkert DP, Hubert JG, Wood JM, Brimble MA. Org. Biomol. Chem. 2013; 11: 5147 2c Motohashi S, Nagase K, Nakakita T, Matsuo T, Yoshida Y, Kawakubo T, Miura M, Toriyama M, Barybin MV. J. Org. Chem. 2011; 76: 3922 3a Tang K.-X, Wang C.-M, Gao T.-H, Chen L, Fan L, Sun L.-P. Adv. Synth. Catal. 2019; 361: 26 3b Pulis AP, Procter DJ. Angew. Chem. Int. Ed. 2016; 55: 9842 4a Kaiser D, Klose I, Oost R, Neuhaus J, Maulide N. Chem. Rev. 2019; 119: 8701 4b Yanagi T, Nogi K, Yorimitsu H. Tetrahedron Lett. 2018; 59: 2951 5 Maryasin B, Kaldre D, Galaverna R, Klose I, Ruider S, Drescher M, Kählig H, González L, Eberlin M, Jurberg I, Maulide N. Chem. Sci. 2018; 9: 4124 6 Yanagi T, Nogi K, Yorimitsu H. Chem. Eur. J. 2020; 26: 783 7a Kaldre D, Maryasin B, Kaiser D, Gajsek O, Gonzalez L, Maulide N. Angew. Chem Int. Ed. 2017; 56: 2212 7b Kaldre D, Klose I, Maulide N. Science 2018; 361: 664 8 Otsuka S, Nogi K, Yorimitsu H. Top. Curr. Chem. 2018; 376: 13 9a Lindner O, Rodefeld L. In Ullmann’s Encyclopedia of Industrial Chemistry . Wiley-VCH; Weinheim: 2010: 269 9b Grundmann C. In Houben-Weyl Methods of Organic Chemistry, 4th ed., Vol. 5/2b. Blome H, Clar E, Fiege H, Garratt PJ, Grundmann C, Gundermann K.-D, Padeken H.-G, Pauson PL, Voelter W, Zander M, Zeller K.-P. Georg Thieme Verlag; Stuttgart: 1981. 354 9c For acid-promoted C–S bond cleavage in sulfoximines, see: Wiezorek S, Lamers P, Bolm C. Chem. Soc. Rev. 2019; 48: 5408 10a Cogan DA, Ellman JA. J. Am. Chem. Soc. 1999; 121: 268 10b Kochi T, Tang TP, Ellman JA. J. Am. Chem. Soc. 2003; 125: 11276 11 Hamel P, Zajac N, Atkinson JG, Girard Y. J. Org. Chem. 1994; 59: 6372 For representative examples of sulfoxide removal in total synthesis using Raney-nickel, see: 12a Klein LL. J. Am. Chem. Soc. 1985; 107: 2573 12b Ohshima T, Xu Y, Takita R, Shimizu S, Zhong D, Shibasaki M. J. Am. Chem. Soc. 2002; 124: 14546 12c Carreño MC, Des Mazery R, Urbano A, Colobert F, Solladié G. Org. Lett. 2004; 6: 297 For representative examples of sulfoxide removal in total synthesis using t-BuLi, see: 13a Mastranzo VM, Yuste F, Ortiz B, Sánchez-Obregón R, Toscano RA, García Ruano JL. J. Org. Chem. 2011; 76: 5036 13b Takiguchi H, Ohmori K, Suzuki K. Chem. Lett. 2011; 40: 1069 13c Vakiti JR, Ghosh S. Tetrahedron Lett. 2014; 55: 6438 14 Pons A, Michalland J, Zawodny W, Chen Y, Tona V, Maulide N. Angew. Chem. Int. Ed. 2019; 58: 17303 15a Singh PK, Field L, Sweetman BJ. J. Org. Chem. 1988; 53: 2608 15b Schöberl A, Gräfje H. Justus Liebigs Ann. Chem. 1958; 617: 71 16 Protodesulfination; General Procedure To a solution of the sulfoxide (0.2 mmol, 1.0 equiv) and 1-octanethiol (0.8 mmol, 4.0 equiv) in CH2Cl2 (0.2 M) in a vial, trifluoromethanesulfonic acid (0.1 mmol, 0.5 equiv) was added and the mixture was stirred for 12 h at 23 °C. The reaction was quenched by the addition of solid NaHCO3, stirred at 23 °C for 10 min, filtered and extracted with CH2Cl2. The resulting organic phase was dried over MgSO4 and concentrated under reduced pressure to give a crude product that was purified by column chromatography (heptane/ethyl acetate). 17 1,3,5-Trimethoxy-2-(methylsulfinyl)benzene (1b) IR (neat): 2943, 1582, 1465, 1458, 1436, 1412, 1340, 1230, 1208, 1187, 1162, 1125, 1086, 1026 cm–1. 1H NMR (600 MHz, CDCl3): δ = 6.12 (s, 2 H), 3.88 (s, 6 H), 3.84 (s, 3 H), 3.04 (s, 3 H). 13C NMR (150 MHz, CDCl3): δ = 164.7, 161.3, 111.5, 91.3, 56.3, 55.7, 38.0. HRMS (ESI+): m/z [M + Na]+ calcd for C10H14O4SNa: 253.0505; found: 253.0512. Zusatzmaterial Zusatzmaterial Supporting Information (PDF)
