Regioselective Functionalization of Arenes Using Iron Triflimide Catalysis

Abstract

Here we present our development of the super Lewis acid, iron(III) triflimide as an activating agent of N-halo- and N-thioaryl succinimides for the regioselective functionalization of arenes. We also describe how the iron(III)-catalyzed halogenation reactions were further exploited by combination with copper(I)-catalyzed Ullmann-type coupling reactions for the development of one-pot, multistep processes, including intermolecular aryl C–H amination. This Account also illustrates intramolecular versions of these one-pot processes for the preparation of benzannulated heterocycles, as well as the application of these methods for the synthesis of biologically active compounds and natural products.

1 Introduction

2 Iron(III)-Catalyzed Halogenation of Arenes

3 One-Pot Intermolecular Aryl C–H Amination

4 One-Pot Intramolecular C–N, C–O, and C–S Bond-Forming Processes

5 Iron(III)-Catalyzed Thioarylation of Arenes

6 Synthesis of Phenoxathiins and Phenothiazines Using Lewis Acid and Lewis Base Catalysis

7 Conclusions

Key words

iron and copper catalysis - halogenation - thioarylation - ­Ullmann coupling - heterocycle synthesis

Publication History

Received: 02 February 2023

Accepted after revision: 21 March 2023

Article published online:
26 April 2023

• References

• 1a Pimlott SL, Sutherland A. Chem. Soc. Rev. 2011; 40: 149
• 1b Sutherland A. Synthesis 2019; 51: 4368
• 2a Sloan NL, Sutherland A. Synthesis 2016; 48: 2969
• 2b Dubost E, McErlain H, Babin V, Sutherland A, Cailly T. J. Org. Chem. 2020; 85: 8300
• 3a Cant AA, Bhalla R, Pimlott SL, Sutherland A. Chem. Commun. 2012; 48: 3993
• 3b Cant AA, Champion S, Bhalla R, Pimlott SL, Sutherland A. Angew. Chem. Int. Ed. 2013; 52: 7829
• 4a Sloan NL, Luthra SK, McRobbie G, Pimlott SL, Sutherland A. RSC Adv. 2017; 7: 54881
• 4b Sloan NL, Luthra SK, McRobbie G, Pimlott SL, Sutherland A. Chem. Commun. 2017; 53: 11008
• 5 Webster S, O’Rourke KM, Fletcher C, Pimlott SL, Sutherland A, Lee A.-L. Chem. Eur. J. 2018; 24: 937
• 6 Molloy JJ, O’Rourke KM, Frias CP, Sloan NL, West MJ, Pimlott SL, Sutherland A, Watson AJ. B. Org. Lett. 2019; 21: 2488
• 7a Larock RC. Comprehensive Organic Transformations, 2nd ed. Wiley-VCH; New York: 1999: 619-626
• 7b Hodgson HH. Chem. Rev. 1947; 40: 251
• 8a Olah GA, Wang Q, Sandford G, Prakash GK. S. J. Org. Chem. 1993; 58: 3194
• 8b Prakash GK. S, Mathew T, Hoole D, Esteves PM, Wang Q, Rasul G, Olah GA. J. Am. Chem. Soc. 2004; 126: 15770
• 8c Wang W, Yang X, Dai R, Yan Z, Wei J, Dou X, Qiu X, Zhang H, Wang C, Liu Y, Song S, Jiao N. J. Am. Chem. Soc. 2022; 144: 13415
• 9 Mo F, Yan JM, Qiu D, Li F, Zhang Y, Wang J. Angew. Chem. Int. Ed. 2010; 49: 2028
• 10 Zhou C.-Y, Li J, Peddibhotla S, Roma D. Org. Lett. 2010; 12: 2104
• 11 Leboeuf D, Ciesielski J, Frontier AJ. Synlett 2014; 25: 399
• 12 Racys DT, Warrilow CE, Pimlott SL, Sutherland A. Org. Lett. 2015; 17: 4782
• 13 Antoniotti S, Dalla V, Duñach E. Angew. Chem. Int. Ed. 2010; 49: 7860
• 14a Cabrero-Antonino JR, Leyva-Pérez A, Corma A. Adv. Synth. Catal. 2010; 352: 1571
• 14b Cabrero-Antonino JR, Leyva-Pérez A, Corma A. Adv. Synth. Catal. 2012; 354: 678
• 14c Cabrero-Antonino JR, Leyva-Pérez A, Corma A. Chem. Eur. J. 2012; 18: 11107
• 14d Cabrero-Antonino JR, Leyva-Pérez A, Corma A. Chem. Eur. J. 2013; 19: 8627
• 15a Earle M, McAuley BJ, Ramani A, Seddon K, Thompson J. WO 02072260, 2002
• 15b Earle MJ, Hakala U, McAuley BJ, Nieuwenhuyzen M, Ramani A, Seddon KR. Chem. Commun. 2004; 1368
• 16 Caveliers V, Everaert H, John CS, Lahoutte T, Bossuyt A. J. Nucl. Med. 2002; 43: 1647
• 17 Kung HF, Kasliwal R, Pan S, Kung M.-P, Mach RH, Guo Y.-Z. J. Med. Chem. 1988; 31: 1039
• 18 Mostafa MA. B, Calder ED. D, Racys DT, Sutherland A. Chem. Eur. J. 2017; 23: 1044
• 19 Cutulle MA, Armel GR, Brosnan JT, Best MD, Kopsell DA, Bruce BD, Bostic HE, Layton DS. J. Agric. Food Chem. 2014; 62: 329
• 20 Mostafa MA. B, Bowley RM, Racys DT, Henry MC, Sutherland A. J. Org. Chem. 2017; 82: 7529
• 21a Brownlee G, Copp FC, Duffin WM, Tonkin IM. Biochem. J. 1943; 37: 572
• 21b Mitchell AG. J. Pharm. Pharmacol. 1964; 16: 533
• 22 Ando K, Kato A, Suzuki S. Biochem. Biophys. Res. Commun. 1970; 39: 1104
• 23a Bohlmann F, Abraham W.-R. Phytochemistry 1979; 18: 839
• 23b Bohlmann F, Knauf W, Misra LN. Tetrahedron 1984; 40: 4987
• 24 Racys DT, Sharif SA. I, Pimlott SL, Sutherland A. J. Org. Chem. 2016; 81: 772
• 25a Henry MC, Mostafa MA. B, Sutherland A. Synthesis 2017; 49: 4586
• 25b Park Y, Kim Y, Chang S. Chem. Rev. 2017; 117: 9247
• 26 Waddell LJ. N, Henry MC, Mostafa MA. B, Sutherland A. Synthesis 2022; 54: 4551
• 27 Xu F, Zhao Y, Zhou H, Li C, Zhang X, Hou T, Qu L, Wei L, Wang J, Liu Y, Liang X. Bioorg. Med. Chem. Lett. 2020; 30: 127650
• 28a Fish PV, Filippakopoulos P, Bish G, Brennan PE, Bunnage ME, Cook AS, Federov O, Gerstenberger BS, Jones H, Knapp S, Marsden B, Nocka K, Owen DR, Philpott M, Picaud S, Primiano MJ, Ralph MJ, Sciammetta N, Trzupek JD. J. Med. Chem. 2012; 55: 9831
• 28b Fish PV, Cook AS, Phillips C, Bent AF, Mills JE. J, Sciammetta N. WO 2013027168 A1, 2013
• 29 Henry MC, McGrory R, Faggyas RJ, Mostafa MA. B, Sutherland A. Org. Biomol. Chem. 2019; 17: 4629
• 30 Klapars A, Antilla JC, Huang X, Buchwald SL. J. Am. Chem. Soc. 2001; 123: 7727
• 31 Palmer WS, Poncet-Montange G, Liu G, Petrocchi A, Reyna N, Subramanian G, Theroff J, Yau A, Kost-Alimova M, Bardenhagen JP, Leo E, Shepard HE, Tieu TN, Shi X, Zhan Y, Zhao S, Barton MC, Draetta G, Toniatti C, Jones P, Do MG, Andersen JN. J. Med. Chem. 2016; 59: 1440

For some examples, see:
• 32a Li J.-J, Mei T.-S, Yu J.-Q. Angew. Chem. Int. Ed. 2008; 47: 6452
• 32b He G, Zhao Y, Zhang S, Lu C, Chen G. J. Am. Chem. Soc. 2012; 134: 3
• 32c Nadres ET, Daugulis O. J. Am. Chem. Soc. 2012; 134: 7
• 32d He G, Lu C, Zhao Y, Nack WA, Chen G. Org. Lett. 2012; 14: 2944
• 32e Mei T.-S, Leow D, Xiao H, Laforteza BN, Yu J.-Q. Org. Lett. 2013; 15: 3058
• 32f Ye X, He Z, Ahmed T, Weise K, Akhmedov NG, Petersen JL, Shi X. Chem. Sci. 2013; 4: 3712
• 32g Wang C, Chen C, Zhang J, Han J, Wang Q, Guo K, Liu P, Guan M, Yao Y, Zhao Y. Angew. Chem. Int. Ed. 2014; 53: 9884
• 33a Wang X, Liu Y, Dai HX, Yu J.-Q. J. Am. Chem. Soc. 2010; 132: 12203
• 33b Wang H, Li G, Engle KM, Yu J.-Q, Davies HW. J. Am. Chem. Soc. 2013; 135: 6774
• 34 Henry MC, Senn HM, Sutherland A. J. Org. Chem. 2019; 84: 346
• 35a Gregson M, Ollis WD, Redman BT, Sutherland IO, Dietrichs HH. Chem. Commun. 1968; 1394
• 35b Gregson M, Ollis WD, Redman BT, Sutherland IO, Dietrichs HH, Gottlieb OR. Phytochemistry 1978; 17: 1395
• 35c Beldjoudi N, Mambu L, Labaïed M, Grellier P, Ramanitrahasimbola D, Rasoanaivo P, Martin MT, Frappier F. J. Nat. Prod. 2003; 66: 1447
• 36 Henry MC, Sutherland A. Org. Lett. 2020; 22: 2766
• 37a González AG, Fraga BM, Hernandez MG, García VP. Phytochemistry 1982; 21: 1826
• 37b Ober AG, Fronczek FR, Fischer NH. J. Nat. Prod. 1985; 48: 242
• 38 Henry MC, Abbinante VM, Sutherland A. Eur. J. Org. Chem. 2020; 2819
• 39a Jacobson P. Ber. Dtsch. Chem. Ges. 1886; 19: 1067
• 39b Downer NK, Jackson YA. Org. Biomol. Chem. 2004; 2: 3039
• 40a Hugerschoff A. Ber. Dtsch. Chem. Ges. 1901; 34: 3130
• 40b Hugerschoff A. Ber. Dtsch. Chem. Ges. 1903; 36: 3121
• 40c Thiel OR, Bernard C, King T, Dilmeghani-Seran M, Bostick T, Larsen RD, Faul MM. J. Org. Chem. 2008; 73: 3508
• 41 Hostier T, Ferey V, Ricci G, Pardo DG, Cossy J. Org. Lett. 2015; 17: 3898
• 42 Nalbandian CJ, Brown ZE, Alvarez E, Gustafson JL. Org. Lett. 2018; 20: 3211
• 43 Dodds AC, Sutherland A. J. Org. Chem. 2021; 86: 5922
• 44 Bruce RB, Turnbull L, Newman J, Pitts J. J. Med. Chem. 1966; 9: 286
• 45 Wolf R, Orni-Wasserlauf R. Intl. J. Dermatol. 2000; 39: 779
• 46 Bang-Andersen B, Ruhland T, Jørgensen M, Smith G, Frederiksen K, Jensen KG, Zhong H, Nielsen SM, Hogg S, Mørk A, Stensbøl TB. J. Med. Chem. 2011; 54: 3206
• 47 Dodds AC, Sutherland A. Org. Biomol. Chem. 2022; 20: 1738
• 48 Dodds AC, Puddu S, Sutherland A. Org. Biomol. Chem. 2022; 20: 5602
• 49a Hartwig JF. Angew. Chem. Int. Ed. 1998; 37: 2046
• 49b Yang BH, Buchwald SL. J. Organomet. Chem. 1999; 576: 125
• 50a Courvoisier S, Ducrot R, Fournel J, Julou LC. C. R. Seances Soc. Biol. Fil. Int. 1957; 151: 689
• 50b Jourdan F, Duchene-Marullaz P, Faucon G, Bouverot P. C. R. Seances Soc. Biol. Fil. Int. 1958; 152: 91
• 50c Apfeldorf M, Bauer HG, McGavack TH. Am. J. Psychiatry 1960; 117: 72