Synlett 2020; 31(10): 1015-1021
DOI: 10.1055/s-0040-1708003
letter
© Georg Thieme Verlag Stuttgart · New York

Pd(0)-Catalyzed Direct Inter- and Intramolecular C–H Functionalization of 4-Carboxyimidazoles

Steven Frippiat
a   Normandie Univ, INSA Rouen, UNIROUEN, CNRS, COBRA (UMR 6014), 76000 Rouen, France   Email: christine.baudequin@univ-rouen.fr   Email: christophe.hoarau@insa-rouen.fr
,
Antoine Peresson
a   Normandie Univ, INSA Rouen, UNIROUEN, CNRS, COBRA (UMR 6014), 76000 Rouen, France   Email: christine.baudequin@univ-rouen.fr   Email: christophe.hoarau@insa-rouen.fr
,
Thibaut Perse
b   Janssen Research & Development, Division of Janssen-Cilag S.A. Campus de Maigremont, BP615, 27106 Val de Reuil Cedex, France
,
Yvan Ramondenc
a   Normandie Univ, INSA Rouen, UNIROUEN, CNRS, COBRA (UMR 6014), 76000 Rouen, France   Email: christine.baudequin@univ-rouen.fr   Email: christophe.hoarau@insa-rouen.fr
,
Cédric Schneider
a   Normandie Univ, INSA Rouen, UNIROUEN, CNRS, COBRA (UMR 6014), 76000 Rouen, France   Email: christine.baudequin@univ-rouen.fr   Email: christophe.hoarau@insa-rouen.fr
,
Olivier Querolle
b   Janssen Research & Development, Division of Janssen-Cilag S.A. Campus de Maigremont, BP615, 27106 Val de Reuil Cedex, France
,
Patrick Angibaud
b   Janssen Research & Development, Division of Janssen-Cilag S.A. Campus de Maigremont, BP615, 27106 Val de Reuil Cedex, France
,
Virginie Poncelet
b   Janssen Research & Development, Division of Janssen-Cilag S.A. Campus de Maigremont, BP615, 27106 Val de Reuil Cedex, France
,
Lieven Meerpoel
c   Janssen Research & Development, Division of Janssen-Cilag a division of Janssen Pharmaceutica NV, Turnhoutseweg 30, 2340 Beerse, Belgium
,
Vincent Levacher
a   Normandie Univ, INSA Rouen, UNIROUEN, CNRS, COBRA (UMR 6014), 76000 Rouen, France   Email: christine.baudequin@univ-rouen.fr   Email: christophe.hoarau@insa-rouen.fr
,
Laurent Bischoff
a   Normandie Univ, INSA Rouen, UNIROUEN, CNRS, COBRA (UMR 6014), 76000 Rouen, France   Email: christine.baudequin@univ-rouen.fr   Email: christophe.hoarau@insa-rouen.fr
,
Christine Baudequin
a   Normandie Univ, INSA Rouen, UNIROUEN, CNRS, COBRA (UMR 6014), 76000 Rouen, France   Email: christine.baudequin@univ-rouen.fr   Email: christophe.hoarau@insa-rouen.fr
,
Christophe Hoarau
a   Normandie Univ, INSA Rouen, UNIROUEN, CNRS, COBRA (UMR 6014), 76000 Rouen, France   Email: christine.baudequin@univ-rouen.fr   Email: christophe.hoarau@insa-rouen.fr
› Author Affiliations
This work has been partially supported by the Institut National des Sciences Appliquées Rouen (INSA), the Rouen University, the Centre National de la Recherche Scientifique (CNRS), the EFRD, the European Interreg IV A France (Channel), and Labex SynOrg (ANR-11-LABX-0029).
Further Information

Publication History

Received: 05 February 2020

Accepted after revision: 29 February 2020

Publication Date:
17 March 2020 (online)


Abstract

The palladium-catalyzed arylation and alkenylation of N-substituted methyl imidazole-4-carboxylates are described through inter- and intramolecular pathways. Both direct C2–H and C5–H arylation and alkenylation proceed under Pd(0)/Cu(I) cooperative catalysis and Pd(0) catalysis, respectively, in low-polarity 1,4-dioxane solvent. The methodology gives access to C2 (hetero)aryl or alkenyl imidazoles as well as innovative C2- and C5-arylated fused imidazoles tricycles with a five- to seven-membered middle ring.

Supporting Information

 
  • References and Notes

    • 1a Wang W, Tang X, Hua F, Ling T.-J, Wan X.-C, Bao G.-H. Org. Lett. 2018; 20: 2672
    • 1b Rodrigues de Carvalho L, de Brito TV, da Simiao Jr CJ, Dias GJ. Jr, de Aguiar MagalhãresD, Guimarães SousaS, Oliveira SilvaR, Pereira da Silva FR, Pereira VasconcelosD. F, Costa VérasL. M, Leite JR. S. A, Santos MartinsD, da Silva MartinsC, Soares de Oliveira J, Barbosa AL. R. Biomed. Pharmacother. 2018; 102: 278
    • 1c Silva VG, Silva RO, Damasceno SR. B, Carvalho NS, Prudêncio RS, Aragão KS, Guimarães MA, Campos SA, Véras LM. C, Godejohann M, Leite JR. S. A, Barbosa AL. R, Medeiros J.-VR. J. Nat. Prod. 2013; 76: 1071
    • 1d Ding H, Roberts AG, Harran PG. Chem. Sci. 2013; 4: 303
    • 1e Sato S, Iwata F, Takeo J, Kawahara H, Kuramoto M, Uno H. Chem. Lett. 2011; 40: 186
    • 1f De Luca L. Curr. Med. Chem. 2006; 13: 1
    • 1g Iinuma Y, Kozawa S, Ishiyama H, Tsuda M, Fukushi E, Kawabata J, Fromont J, Kobayashi J. J. Nat. Prod. 2005; 68: 1109
    • 1h Fresneda PM, Molina P, Sanz MA. Tetrahedron Lett. 2001; 42: 851
  • 2 Zhang L, Peng X.-M, Damu GL. V, Geng R.-X, Zhou C.-H. Med. Res. Rev. 2014; 34: 340

    • For recent reviews, see:
    • 3a Chen W.-C, Zhu Z.-L, Lee C.-S. Adv. Opt. Mater. 2018; 6: 1800258
    • 3b Anderson EB, Long TE. Polymer 2010; 51: 2447

      For reviews, see:
    • 4a Liu J.-Q, Gou X.-X, Han Y.-F. Chem. Asian J. 2018; 13: 2257
    • 4b Garrison JC, Youngs WJ. Chem. Rev. 2005; 105: 3978
    • 4c Braband H, Kueckmann T, Theresa I, Abram U. J. Organomet. Chem. 2005; 690: 5421
    • 4d Scott NM, Nolan SP. Eur. J. Inorg. Chem. 2005; 1815
    • 4e Herrmann WA. Angew. Chem. Int. Ed. 2002; 41: 1290

      For recent reviews, see:
    • 5a Wang N, Xu J, Lee JK. Org. Biomol. Chem. 2018; 16: 8230
    • 5b Wang Z, Pan D, Li T, Jin Z. Chem. Asian J. 2018; 13: 2149

      For leading references, see:
    • 6a Wilkes JS, Zaworotko MJ. J. Chem. Soc., Chem. Commun. 1992; 965
    • 6b Welton T. Chem. Rev. 1999; 99: 2071
    • 6c Wasserscheid P, Keim W. Angew. Chem. Int. Ed. 2000; 39: 3772
    • 6d Dupont J, de Souza RF, Suarez PA. Z. Chem. Rev. 2002; 102: 3667
    • 6e Karimi B, Tavakolian M, Akbari M, Mansouri F. ChemCatChem 2018; 10: 3173

      For recent reviews, see:
    • 7a Rossi R, Angelici G, Casotti G, Manzini C, Lessi M. Adv. Synth. Catal. 2019; 361: 2737
    • 7b Gulevich AV, Dudnik AS, Chernyak N, Gevorgyan V. Chem. Rev. 2013; 113: 3084
    • 7c Kamijo S, Yamamoto Y. Chem. Asian J. 2007; 2: 568

      For selected C–H arylation of imidazoles or their ring-fused analogues catalyzed by rhodium, copper, or nickel metals, see:
    • 8a Lewis JC, Berman AM, Bergman RG, Ellman JA. J. Am. Chem. Soc. 2008; 130: 2493
    • 8b Lewis JC, Bergman RG, Ellman JA. Acc. Chem. Res. 2008; 41: 1013
    • 8c Lewis JC, Wu JY, Bergman RG, Ellman JA. Angew. Chem. Int. Ed. 2006; 45: 1589
    • 8d Lewis JC, Wiedemann SH, Bergman RG, Ellman JA. Org. Lett. 2004; 6: 35
    • 8e Zhao D, Wang W, Yang F, Lan J, Yang L, Gao G, You J. Angew. Chem. Int. Ed. 2009; 48: 3296
    • 8f Daugulis O, Do H.-Q, Shabashov D. Acc. Chem. Res. 2009; 42: 1074
    • 8g Do H.-Q, Khan RM. K, Daugulis O. J. Am. Chem. Soc. 2008; 130: 15185
    • 8h Do H.-Q, Daugulis O. J. Am. Chem. Soc. 2007; 129: 12404
    • 8i Muto K, Hatakeyama T, Yamaguchi J, Itami K. Chem. Sci. 2015; 6: 6792

      For reviews on this topic, see:
    • 9a Ref. 7a.
    • 9b Bellina F, Rossi R. Adv. Synth. Catal. 2010; 352: 1223
    • 9c De Ornellas S, Storr TE, Williams TJ, Baumann CG, Fairlamb IJ. S. Curr. Org. Synth. 2011; 8: 79

      For palladium-catalyzed intramolecular direct arylation of imidazole, see:
    • 10a Xu X, Zhao L, Li Y, Soulé J.-F, Doucet H. Adv. Synth. Catal. 2015; 357: 2869
    • 10b Laha JK, Dayal N, Singh S, Bhimpuria R. Eur. J. Org. Chem. 2014; 5469
    • 10c Laha JK, Cuny GD. J. Org. Chem. 2011; 76: 8477
    • 10d Koubachi J, Berteina-Raboin S, Mouaddib A, Guillaumet G. Tetrahedron 2010; 66: 1937
    • 10e Majumdar KC, Debnath P, Taher A, Pal AK. Can. J. Chem. 2008; 86: 325
    • 10f Lee HS, Kim SH, Gowrisankar S, Kim JN. Tetrahedron 2008; 64: 7183
    • 10g Arai N, Takahashi M, Mitani M, Mori A. Synlett 2006; 3170
    • 10h Gracias V, Gasiecki AF, Pagano TG, Djuric SW. Tetrahedron Lett. 2006; 47: 8873
    • 10i Delest B, Tisserand J.-Y, Robert J.-M, Nourrisson M.-R, Pinson P, Duflos M, Le Baut G, Renard P, Pfeiffer B. Tetrahedron 2004; 60: 6079
    • 10j Kuroda T, Suzuki F. Tetrahedron Lett. 1991; 32: 6915

      For palladium-catalyzed intermolecular direct arylation of imidazole derivatives, see:
    • 11a Vellakkaran M, Lingayya R, Kumar BN, Nagaiah K, Poornachandra Y, Kumar CG. RSC Adv. 2015; 5: 8057
    • 11b Grosse S, Pillard C, Massip S, Marchivie M, Jarry C, Bernard P, Guillaumet G. J. Org. Chem. 2015; 80: 8539
    • 12a Lessi M, Panzetta G, Marianetti G, Bellina F. Synthesis 2017; 49: 4676
    • 12b Perego LA, Grimaud L, Bellina F. Adv. Synth. Catal. 2016; 358: 597
    • 12c Bellina F, Lessi M, Manzini C. Eur. J. Org. Chem. 2013; 5621
    • 12d Bellina F, Cauteruccio S, Di Fiore A, Marchetti C, Rossi R. Tetrahedron 2008; 64: 6060
    • 12e Bellina F, Cauteruccio S, Di Fiore A, Rossi R. Eur. J. Org. Chem. 2008; 5436
    • 12f Bellina F, Cauteruccio S, Rossi R. Curr. Org. Chem. 2008; 12: 774
    • 12g Bellina F, Calandri C, Cauteruccio S, Rossi R. Tetrahedron 2007; 63: 1970
    • 12h Bellina F, Cauteruccio S, Rossi R. J. Org. Chem. 2007; 72: 8543
    • 12i Bellina F, Cauteruccio S, Mannina L, Rossi R, Viel S. Eur. J. Org. Chem. 2006; 693
    • 12j Bellina F, Cauteruccio S, Mannina L, Rossi R, Viel S. J. Org. Chem. 2005; 70: 3997
  • 13 Joo JM, Touré BB, Sames D. J. Org. Chem. 2010; 75: 4911
  • 14 Kuroda T, Suzuki F. Tetrahedron Lett. 1991; 32: 6915
    • 15a Martin T, Verrier C, Hoarau C, Marsais F. Org. Lett. 2008; 10: 2909
    • 15b Verrier C, Martin T, Hoarau C, Marsais F. J. Org. Chem. 2008; 73: 7383
    • 15c Roger J, Verrier C, Le Goff R, Hoarau C, Doucet H. ChemSusChem 2009; 2: 951
    • 15d Verrier C, Hoarau C, Marsais F. Org. Biomol. Chem. 2009; 7: 647
    • 15e Verrier C, Fiol-Petit C, Hoarau C, Marsais F. Org. Biomol. Chem. 2011; 9: 6215
    • 15f Théveau L, Verrier C, Lassalas P, Martin T, Dupas G, Querolle O, Van Hijfte L, Marsais F, Hoarau C. Chem. Eur. J. 2011; 17: 14451
    • 15g Théveau L, Querolle O, Dupas G, Hoarau C. Tetrahedron 2013; 69: 4375
  • 16 Thireau J, Schneider C, Baudequin C, Gaurrand S, Angibaud P, Meerpoel L, Levacher V, Querolle O, Hoarau C. Eur. J. Org. Chem. 2017; 2491

    • For recent reviews, see:
    • 17a Cai X.-h, Yang M, Xie B. Curr. Org. Chem. 2018; 22: 1906
    • 17b Zhang T, Wang N.-X, Xing Y. J. Org. Chem. 2018; 83: 7559
    • 17c Hosseinian A, Nasab FA. H, Ahmadi S, Rahmani Z, Vessally E. RSC Adv. 2018; 8: 26383
    • 17d Schwarz J, König B. Green Chem. 2018; 20: 323
    • 17e Perry GJ. P, Larrosa I. Eur. J. Org. Chem. 2017; 3517
    • 17f Wie Y, Hu P, Zhang M, Su W. Chem. Rev. 2017; 117: 8864
    • 17g Jin Y, Fu H. Asian J. Org. Chem. 2017; 6: 368
    • 17h Li H, Miao T, Wang M, Li P, Wang L. Synlett 2016; 27: 1635
    • 18a Allin SM, Bowman WR, Elsegood MR. J, McKee V, Karim R, Rahman SS. Tetrahedron 2005; 61: 2689
    • 18b Aldabbagh F, Bowman WR, Mann E, Slawin AM. Z. Tetrahedron 1999; 55: 8111
  • 19 Two regioisomers were obtained. However, concerning this study only methyl N-alkylated imidazole-4-carboxylates were evaluated.

    • For recent references, see:
    • 20a Baba K, Masuya Y, Chatani N, Tobisu M. Chem. Lett. 2017; 46: 1296
    • 20b Zhou H, Li J, Yang H, Xia C, Jiang G. Org. Lett. 2015; 17: 4628
    • 20c Zhou Y, Gan Z, Su B, Li J, Duan Z, Mathey F. Org. Lett. 2015; 17: 5722
    • 20d Baba K, Tobisu M, Chatani N. Org. Lett. 2015; 17: 70
    • 20e Karthik V, Gupta V, Anantharaman G. Organometallics 2015; 34: 3713
    • 20f Baba K, Tobisu M, Chatani N. Angew. Chem. Int. Ed. 2013; 52: 11892
    • 20g Li Z, Zhou H, Xu J, Wu X, Yao H. Tetrahedron 2013; 69: 3281
    • 20h Ma M.-T, Lu J.-M. Tetrahedron 2013; 69: 2102
  • 21 See the Supporting Information for more details.
  • 22 General Procedure for Pd-Catalyzed Intermolecular Direct C2–H Arylation of Methyl N-Benzyl-1H-imidazole 4-carboxylate under Thermic ConditionsMethyl 1-benzyl-1H-imidazole-4-carboxylate (1a, 80 mg, 0.37 mmol, 1 equiv), the requisite halide 2 (1.2 equiv), Pd(OAc)2 (18 μmol, 5 mol%), PPh3 (37 μmol, 10 mol%), CuI (0.74 mmol, 2 equiv), and anhydrous DBU (0.74 mmol, 2 equiv) were placed in a dry sealed tube containing a magnetic stir bar. The tube was evacuated and back-filled with nitrogen three times before adding anhydrous 1,4-dioxane (2.5 mL). The tube was sealed and heated to 140 °C for 18 h. The reaction was filtered through a Celite® pad (washing with DCM and EtOAc). The solvents were removed under reduced pressure, and the crude product was then purified by column chromatography (DCM to DCM/EtOAc, 9:1).
  • 23 Compound 3a was prepared according to the general procedure. The crude product was purified by flash chromatography to afford 3a in 76% yield using the aryl bromide and 95% yield using the aryl iodide as a pale yellow solid; mp 89–90 °C. 1H NMR (300 MHz, CDCl3): δ = 7.64 (s, 1 Him, H5), 7.46 (d, J = 8.0 Hz, 2 Harom), 7.35–7.33 (m, 3 Hbenzyl), 7.22 (d, J = 8.0 Hz, 2 Harom), 7.09–7.07 (m, 2 Hbenzyl), 5.19 (s, 2 H), 3.89 (s, 3 H, OMe), 2.38 (s, 3 H, CH3). 13C NMR (75 MHz, CDCl3): δ = 163.5 (C=O), 149.5 (C2, Cqim), 139.7 (C4′, Cqarom), 135.9 (C1′, Cqbenzyl), 132.9 (C4im, Cq), 129.3 (2 × CH), 129.2 (2 × CH), 129.1 (2 × CH), 128.4 (CHbenzyl), 127.1 (C5, CHim), 126.9 (2 × CHbenzyl), 126.5 (Cq), 51.8 (OCH3), 51.0 (NCH2), 21.4 (CH3). IR (ATR): 3125, 3079, 2920, 2850, 1689, 1549, 1330, 1227, 1004, 725 cm–1. HRMS: Anal. Calcd for C19H19N2O2 [M + H]+: 307.1447; found: 307.1455.
    • 24a Vabre R, Chevot F, Legraverend M, Piguel S. J. Org. Chem. 2011; 76: 9542
    • 24b Vabre R, Legraverend M, Piguel S. Dyes Pigm. 2014; 105: 145
    • 24c Baladi T, Granzhan A, Piguel S. Eur. J. Org. Chem. 2016; 2421
  • 25 Sahnoun S, Messaoudi S, Brion J.-D, Alami M. Eur. J. Org. Chem. 2010; 6097
  • 26 Lee W.-C, Wang T.-H, Ong T.-G. Chem. Commun. 2014; 50: 3671
    • 27a Muselli M, Baudequin C, Perrio C, Hoarau C, Bischoff L. Chem. Eur. J. 2016; 22: 5520
    • 27b Muselli M, Baudequin C, Hoarau C, Bischoff L. Chem. Commun. 2015; 51: 745
    • 28a Gorelsky SI. Coord. Chem. Rev. 2013; 257: 153
    • 28b Gorelsky SI, Lapointe D, Fagnou K. J. Org. Chem. 2012; 77: 658
  • 29 Iaroshenko VO, Gevorgyan A, Mkrtchyan S, Arakelyan K, Grigoryan T, Yedoyan J, Villinger A, Langer P. J. Org. Chem. 2015; 80: 2103