1.10 The Pentafluorosulfanyl Group (SF₅)

Abstract

The pentafluorosulfanyl group imparts exceptional thermal, chemical, and metabolic stability to organic scaffolds. Despite being first described seven decades ago, it remains an under-utilized motif in organofluorine chemistry, primarily due to a lack of efficient synthetic routes that proceed under mild reaction conditions. Nonetheless, the renewed interest in pentafluorosulfanyl scaffolds over the last decade has enabled the preparation of important pentafluorosulfanyl building blocks. Herein, the major synthetic strategies for the preparation of pentafluoro-λ6-sulfanyl-containing compounds are reviewed, including the synthesis of (pentafluorosulfanyl)arenes via oxidative halogenation and the direct pentafluorosulfanylation of aliphatic cores, achieved mainly using pentafluorosulfanyl chloride as a reagent.

Schlüsselwörter

pentafluorosulfanyl compounds - fluorine - fluorination - sulfur - oxidative fluorination - chlorine - chlorotetrafluorosulfanyl compounds - arenes - aliphatic compounds - unsaturated compounds

• 1 Weinhold F, Landis CR. Valency and Bonding: A Natural Bond Orbital Donor–Acceptor Perspective. Cambridge University Press; Cambridge 2005

• 2 Dolbier Jr WR. Guide to Fluorine NMR for Organic Chemists. Wiley; Hoboken, NJ 2016

• 3 Savoie PR, Welch JT. Chem. Rev. 2015; 115: 1130

• 4 Westphal MV, Wolfstädter BT, Plancher J.-M, Gatfield J, Carreira EM. ChemMedChem 2015; 10: 461

• 5 Joliton A, Plancher J.-M, Carreira EM. Angew. Chem. Int. Ed. 2016; 55: 2113

• 6 Kordnezhadian R, Li BY, Zogu A, Demaerel J, De Borggraeve WM, Ismalaj E. Chem.–Eur. J. 2022; 28 e202201491

• 7 Barnes-Seeman D, Jain M, Bell L, Ferreira S, Cohen S, Chen X.-H, Amin J, Snodgrass B, Hatsis P. ACS Med. Chem. Lett. 2013; 4: 514

• 8 Silvey GA, Cady GH. J. Am. Chem. Soc. 1950; 72: 3624

• 9 Roberts HL, Ray NH. J. Chem. Soc. 1960; 665

• 10 Pashinnik VE, Martyniuk EG, Tabachuk MR, Shermolovich YG, Yagupolskii LM. Synth. Commun. 2003; 33: 2505

• 11 Umemoto T. WO 2010014665, 2010

• 12 Pitts CR, Bornemann D, Liebing P, Santschi N, Togni A. Angew. Chem. Int. Ed. 2019; 58: 1950

• 13 Sheppard WA. J. Am. Chem. Soc. 1960; 82: 4751

• 14 Sheppard WA. J. Am. Chem. Soc. 1962; 84: 3064

• 15 Williams AG, Foster NR. WO 1994022817, 1994

• 16 Bowden RD, Comina PJ, Greenhall MP, Kariuki BM, Loveday A, Philp D. Tetrahedron 2000; 56: 3399

• 17 Ou X, Janzen AF. J. Fluorine Chem. 2000; 101: 279

• 18 Ajenjo J, Klepetářová B, Greenhall M, Bím D, Culka M, Rulíšek L, Beier P. Chem.–Eur. J. 2019; 25: 11375

• 19 Ou X, Bernard GM, Janzen AF. Can. J. Chem. 1997; 75: 1878

• 20 Kordnezhadian R, Zogu A, Borgarelli C, Van Lommel R, Demaerel J, De Borggraeve WM, Ismalaj E. Chem.–Eur. J. 2023; 29 e202300361

• 21 Umemoto T, Garrick LM, Saito N. Beilstein J. Org. Chem. 2012; 8: 461

• 22 Morim A, Guldner GT. Chlorine Gas Toxicity. StatPearls Publishing; Treasure Island, FL 2023. Zugriff am . 24 05.2 unter: https://www.ncbi.nlm.nih.gov/books/NBK537213/

• 23 Kanishchev OS, Dolbier Jr WR. Angew. Chem. Int. Ed. 2015; 54: 280

• 24 Kosobokov M, Cui B, Balia A, Matsuzaki K, Tokunaga E, Saito N, Shibata N. Angew. Chem. Int. Ed. 2016; 55: 10781

• 25 Saidalimu I, Liang Y, Niina K, Tanagawa K, Saito N, Shibata N. Org. Chem. Front. 2019; 6: 1157

• 26 Wang L, Cornella J. Angew. Chem. Int. Ed. 2020; 59: 23510

• 27 Wang L, Ni S, Cornella J. Synthesis 2021; 53: 4308

• 28 Cui B, Jia S, Tokunaga E, Saito N, Shibata N. Chem. Commun. (Cambridge) 2017; 53: 12738

• 29 Lummer K, Ponomarenko MV, Röschenthaler G.-V, Bremer M, Beier P. J. Fluorine Chem. 2014; 157: 79

• 30 Tanagawa K, Zhao Z, Saito N, Shibata N. Bull. Chem. Soc. Jpn. 2021; 94: 1682

• 31 Gilbert A, Paquin J.-F. J. Fluorine Chem. 2019; 221: 70

• 32 Sidebottom HW, Tedder JM, Walton JC. Trans. Faraday Soc. 1969; 65: 2103

• 33 Shou J.-Y, Xu X.-H, Qing F.-L. Angew. Chem. Int. Ed. 2021; 60: 15271

• 34 Taponard A, Jarrosson T, Khrouz L, Médebielle M, Broggi J, Tlili A. Angew. Chem. Int. Ed. 2022; 61 e202204623

• 35 Kordnezhadian R, De Bels T, Su K, Van Meervelt L, Ismalaj E, Demaerel J, De Borggraeve WM. Org. Lett. 2023; 25: 8947

• 36 Case JR, Ray NH, Roberts HL. J. Chem. Soc. 1961; 2066

• 37 Gage JC. Br. J. Ind. Med. 1970; 27: 1

• 38 Brel VK. Synthesis 2006; 339

• 39 Ponomarenko MV, Serguchev YA, Röschenthaler G.-V. J. Fluorine Chem. 2010; 131: 270

• 40 Ponomarenko MV, Kalinovich N, Serguchev YA, Bremer M, Röschenthaler G.-V. J. Fluorine Chem. 2012; 135: 68

• 41 Aït-Mohand S, Dolbier Jr WR. Org. Lett. 2002; 4: 3013

• 42 Sergeeva TA, Dolbier Jr WR. Org. Lett. 2004; 6: 2417

• 43 Dolbier Jr WR, Mitani A, Xu W, Ghiviriga I. Org. Lett. 2006; 8: 5573

• 44 Dolbier Jr WR, Mitani A, Warren RD. Tetrahedron Lett. 2007; 48: 1325

• 45 Ponomarenko MV, Lummer K, Fokin AA, Serguchev YA, Bassil BS, Röschenthaler G.-V. Org. Biomol. Chem. 2013; 11: 8103

• 46 Shou J.-Y, Qing F.-L. Angew. Chem. Int. Ed. 2022; 61 e202208860

• 47 Gilbert A, Langowski P, Paquin J.-F. Tetrahedron 2021; 98: 132424

• 48 Lefebvre G, Charron O, Cossy J, Meyer C. Org. Lett. 2021; 23: 5491

• 49 Mastalerz V, Lam K, Paquin J.-F. J. Fluorine Chem. 2023; 268: 110113

• 50 Winter R. US 9868637, 2009

• 51 Berry A, Fox W. J. Org. Chem. 1978; 43: 365

• 52 Dolbier Jr WR, Aït-Mohand S, Schertz TD, Sergeeva TA, Cradlebaugh JA, Mitani A, Gard GL, Winter RW, Thrasher JS. J. Fluorine Chem. 2006; 127: 1302

• 53 Lim DS, Ngo SC, Lal SG, Minnich KE, Welch JT. Tetrahedron Lett. 2008; 49: 5662

• 54 Lim DS, Lin JH, Welch JT. Eur. J. Org. Chem. 2012; 3946

• 55 Kraemer Y, Ghiazza C, Ragan AN, Ni S, Lutz S, Neumann EK, Fettinger JC, Nöthling N, Goddard R, Cornella J, Pitts CR. Angew. Chem. Int. Ed. 2022; 61 e202211892

• 56 Kraemer Y, Buldt JA, Kong W.-Y, Stephens AM, Ragan AN, Park S, Haidar ZC, Patel AH, Shey R, Dagan R. Angew. Chem. Int. Ed. 2024; 63 e202319930

• 57 Rombach D, Wagenknecht H.-A. Angew. Chem. Int. Ed. 2020; 59: 300

• 58 Birepinte M, Champagne PA, Paquin J.-F. Angew. Chem. Int. Ed. 2022; 61 e202112575

• 59 Hoover F, Coffman D. J. Org. Chem. 1964; 29: 3567

• 60 Nguyen TM, Popek L, Matchavariani D, Blanchard N, Bizet V, Cahard D. Org. Lett. 2024; 26: 365

• 61 Gilbert A, Langowski P, Delgado M, Chabaud L, Pucheault M, Paquin J.-F. Beilstein J. Org. Chem. 2020; 16: 3069

• 62 Lopez SE, Mitani A, Pena P, Ghiviriga I, Dolbier Jr WR. J. Fluorine Chem. 2015; 176: 121

• 63 Debrauwer V, Leito I, Lõkov M, Tshepelevitsh S, Parmentier M, Blanchard N, Bizet V. ACS Org. Inorg. Au 2021; 1: 43

• 64 Popek L, Cihan M, Blanchard N, Bizet V. Angew. Chem. Int. Ed. 2024; 63 e202315909

• 65 Popek L, Cabrera-Trujillo JJ, Debrauwer V, Blanchard N, Miqueu K, Bizet V. Angew. Chem. Int. Ed. 2023; 62 e202300685

• 66 Nguyen TM, Legault CY, Blanchard N, Bizet V, Cahard D. Chem.–Eur. J. 2023; 29 e202302914

• 67 Cloutier M, Roudias M, Paquin J.-F. Org. Lett. 2019; 21: 3866

• 68 Shou J.-Y, Xu X.-H, Qing F.-L. J. Fluorine Chem. 2022; 261: 110018