Synthesis 2017; 49(01): 127-134
DOI: 10.1055/s-0036-1588890
paper
© Georg Thieme Verlag Stuttgart · New York

Ruthenium(II)-Catalyzed C−H Methylation with Trifluoroborates

Marlon Daniel Lima Tonin
Institut für Organische und Biomolekulare Chemie, Georg-August-Universität, Tammannstraße 2, 37077 Göttingen, Germany   Email: lutz.ackermann@chemie.uni-goettingen.de
,
Daniel Zell
Institut für Organische und Biomolekulare Chemie, Georg-August-Universität, Tammannstraße 2, 37077 Göttingen, Germany   Email: lutz.ackermann@chemie.uni-goettingen.de
,
Valentin Müller
Institut für Organische und Biomolekulare Chemie, Georg-August-Universität, Tammannstraße 2, 37077 Göttingen, Germany   Email: lutz.ackermann@chemie.uni-goettingen.de
,
Lutz Ackermann*
Institut für Organische und Biomolekulare Chemie, Georg-August-Universität, Tammannstraße 2, 37077 Göttingen, Germany   Email: lutz.ackermann@chemie.uni-goettingen.de
› Author Affiliations
Further Information

Publication History

Received: 31 July 2016

Accepted After revision: 06 September 2016

Publication Date:
26 September 2016 (online)


These authors contributed equally

Dedicated to Professor Dieter Enders

Abstract

A cationic ruthenium(II)-complex enabled unprecedented C–H methylations on indoles and pyrroles. The versatile catalyst proved to be widely applicable and delivered the methylated heteroarenes with excellent levels of positional selectivity and ample substrate scope. The robustness of the catalysts was reflected by the challenging racemization-free C–H methylation of (S)-tryptophan.

Supporting Information

 
  • References


    • For selected contributions, see:
    • 1a Kuntz KW, Campbell JE, Keilhack H, Pollock RM, Knutson SK, Porter-Scott M, Richon VM, Sneeringer CJ, Wigle TJ, Allain CJ, Majer CR, Moyer MP, Copeland RA, Chesworth R. J. Med. Chem. 2016; 59: 1556
    • 1b Schönherr H, Cernak T. Angew. Chem. Int. Ed. 2013; 52: 12256
    • 1c Leung CS, Leung SS. F, Tirado-Rives J, Jorgensen WL. J. Med. Chem. 2012; 55: 4489
    • 1d Barreiro EJ, Kümmerle AE, Fraga CA. M. Chem. Rev. 2011; 111: 5215 ; and references cited therein

      For representative examples, see:
    • 2a Southall NT, Dill KA, Haymet AD. J. J. Phys. Chem. B 2002; 106: 521
    • 2b Andrews PR, Craik DJ, Martin JL. J. Med. Chem. 1984; 27: 1648

      Recent examples:
    • 3a Bockus AT, Schwochert JA, Pye CR, Townsend CE, Sok V, Bednarek MA, Lokey RS. J. Med. Chem. 2015; 58: 7409
    • 3b Schärfer C, Schulz-Gasch T, Ehrlich H.-C, Guba W, Rarey M, Stahl M. J. Med. Chem. 2013; 56: 2016
    • 3c Quancard J, Bollbuck B, Janser P, Angst D, Berst F, Buehlmayer P, Streiff M, Beerli C, Brinkmann V, Guerini D, Smith PA, Seabrook TJ, Traebert M, Seuwen K, Hersperger R, Bruns C, Bassilana F, Bigaud M. Chem. Biol. 2012; 19: 1142
    • 3d Bahl A, Barton P, Bowers K, Caffrey MV, Denton R, Gilmour P, Hawley S, Linannen T, Luckhurst CA, Mochel T, Perry MW. D, Riley RJ, Roe E, Springthorpe B, Stein L, Webborn P. Bioorg. Med. Chem. Lett. 2012; 22: 6694
    • 3e Boehringer M, Fischer H, Hennig M, Hunziker D, Huwyler J, Kuhn B, Loeffler BM, Luebbers T, Mattei P, Narquizian R, Sebokova E, Sprecher U, Wessel HP. Bioorg. Med. Chem. Lett. 2010; 20: 1106
    • 3f Gomtsyan A, Bayburt EK, Keddy R, Turner SC, Jinkerson TK, Didomenico S, Perner RJ, Koenig JR, Drizin I, McDonald HA, Surowy CS, Honore P, Mikusa J, Marsh KC, Wetter JM, Faltynek CR, Lee C.-H. Bioorg. Med. Chem. Lett. 2007; 17: 3894 ; and references cited therein
    • 4a Whisler MC, MacNeil S, Snieckus V, Beak P. Angew. Chem. Int. Ed. 2004; 43: 2206
    • 4b Snieckus V. Chem. Rev. 1990; 90: 879
    • 5a Rudolph A, Lautens M. Angew. Chem. Int. Ed. 2009; 48: 2656
    • 5b Doucet H. Eur. J. Org. Chem. 2008; 2013
    • 5c Frisch AC, Beller M. Angew. Chem. Int. Ed. 2005; 44: 674

      Representative recent reviews on C–H activation:
    • 6a Kim J.-K, Shin K, Chang S. Top. Organomet. Chem. 2016; 55: 29
    • 6b Borie C, Ackermann L, Nechab M. Chem. Soc. Rev. 2016; 45: 1368
    • 6c Daugulis O, Roane J, Tran LD. Acc. Chem. Res. 2015; 48: 1053
    • 6d Li J, Ackermann L. Nat. Chem. 2015; 7: 686
    • 6e Girard S.-A, Knauber T, Li C.-J. Angew. Chem. Int. Ed. 2014; 53: 74
    • 6f Gao K, Yoshikai H. Acc. Chem. Res. 2014; 47: 1208
    • 6g Rouquet G, Chatani N. Angew. Chem. Int. Ed. 2013; 52: 11726
    • 6h Satoh T, Miura M. Chem. Eur. J. 2010; 16: 11212
    • 6i Giri R, Shi B.-F, Engle K.-M, Maugel N, Yu J.-Q. Chem. Soc. Rev. 2009; 38: 3242
    • 6j Ackermann L, Vicente R, Kapdi A. Angew. Chem. Int. Ed. 2009; 48: 9792
    • 6k Bergman RG. Nature (London) 2007; 446: 391 ; and references cited therein
  • 7 Ackermann L. Chem. Commun. 2010; 46: 4866

    • For recent progress, mostly in palladium and rhodium catalysis, see:
    • 8a Tu D, Cheng X, Gao Y, Yang P, Ding Y, Jiang C. Org. Biomol. Chem. 2016; 14: 7443
    • 8b Graczyk K, Haven T, Ackermann L. Chem. Eur. J. 2015; 21: 8812
    • 8c Wang H, Yu S, Qi Z, Li X. Org. Lett. 2015; 17: 2812
    • 8d Pan F, Lei Z.-Q, Wang H, Li H, Sun J, Shi Z.-J. Angew. Chem. Int. Ed. 2013; 52: 2063
    • 8e Neufeldt SR, Seigerman CK, Sanford MS. Org. Lett. 2013; 15: 2302
    • 8f Yao B, Song R.-J, Liu Y, Xie Y.-X, Li J.-H, Wang M.-K, Tang R.-Y, Zhang X.-G, Deng C.-L. Adv. Synth. Catal. 2012; 354: 1890
    • 8g Zhao Z, Chen G. Org. Lett. 2011; 13: 4850
    • 8h Romero-Revilla JA, Garcia-Rubia A, Arrayas RG, Fernandez-Ibanez MA, Carretero JC. J. Org. Chem. 2011; 76: 9525
    • 8i Dai H.-X, Stepan AF, Plummer MS, Zhang Y.-H, Yu J.-Q. J. Am. Chem. Soc. 2011; 133: 7222
    • 8j Chen Q, Ilies L, Yoshikai N, Nakamura E. Org. Lett. 2011; 13: 3232
    • 8k Verrier C, Hoarau C, Marsais F. Org. Biomol. Chem. 2009; 7: 647
    • 8l Zhang Y, Feng J, Li C.-J. J. Am. Chem. Soc. 2008; 130: 2900
    • 8m Giri R, Maugel N, Li J, Wang D, Breazzano SP, Saunders LB, Yu J.-Q. J. Am. Chem. Soc. 2007; 129: 3510
    • 8n Chen X, Li J, Hao X, Goodhue CE, Yu J.-Q. J. Am. Chem. Soc. 2006; 128: 78
    • 8o McCallum JS, Gasdaska JR, Liebeskind LS, Tremont SJ. Tetrahedron Lett. 1989; 30: 4085
    • 8p Tremont SJ, Rahman HU. J. Am. Chem. Soc. 1984; 106: 5759

      Recent reviews on and examples of ruthenium-catalyzed C–H functionalization:
    • 9a Ackermann L. Org. Process Res. Dev. 2015; 18: 260
    • 9b Sarkar SD, Liu W, Kozhushkov SI, Ackermann L. Adv. Synth. Catal. 2014; 356: 1461
    • 9c Thirunavukkarasu VS, Kozhushkov SI, Ackermann L. Chem. Commun. 2014; 50: 29
    • 9d Li B, Dixneuf PH. Chem. Soc. Rev. 2013; 42: 5744
    • 9e Kozhushkov SI, Ackermann L. Chem. Sci. 2013; 4: 886
    • 9f Arockiam PB, Bruneau C, Dixneuf PH. Chem. Rev. 2012; 112: 5879
    • 9g Sollert C, Devaraj K, Orthaber A, Gates PJ, Pilarski LT. Chem. Eur. J. 2015; 21: 5380
    • 9h Tiwari VK, Kamal N, Kapur M. Org. Lett. 2015; 17: 1766
    • 9i Hubrich J, Himmler T, Rodefeld L, Ackermann L. Adv. Synth. Catal. 2015; 357: 474
    • 9j Chinnagolla RK, Jeganmohan M. Chem. Commun. 2014; 50: 2442
    • 9k Chinnagolla RK, Jeganmohan M. Org. Lett. 2012; 14: 5246
    • 9l Li H, Xu Y, Shi E, Wei W, Suo X, Wan X. Chem. Commun. 2011; 47: 7880
    • 9m Li H, Wei W, Xu Y, Zhang C, Wan X. Chem. Commun. 2011; 47: 1497
    • 9n Ackermann L, Vicente R. Top. Curr. Chem. 2010; 292: 211
    • 10a Hubrich J, Ackermann L. Eur. J. Org. Chem. 2016; 3700
    • 10b Hubrich J, Himmler T, Rodefeld L, Ackermann L. ACS Catal. 2015; 5: 4089
    • 10c Li J, Warratz S, Zell D, De Sarkar S, Ishikawa EE, Ackermann L. J. Am. Chem. Soc. 2015; 137: 13894
    • 10d Hofmann N, Ackermann L. J. Am. Chem. Soc. 2013; 135: 5877
    • 10e Kozhushkov SI, Potukuchi HK, Ackermann L. Catal. Sci. Technol. 2013; 3: 562
    • 10f Ackermann L, Hofmann N, Vicente R. Org. Lett. 2011; 13: 1875
    • 10g Ackermann L, Novák P, Vicente R, Hofmann N. Angew. Chem. Int. Ed. 2009; 48: 6045
  • 11 Zhang F, Spring DR. Chem. Soc. Rev. 2014; 43: 6906

    • Examples from our laboratories:
    • 13a Zhu Y, Bauer M, Ackermann L. Chem. Eur. J. 2015; 21: 9980
    • 13b Zhu Y, Bauer M, Ploog J, Ackermann L. Chem. Eur. J. 2014; 20: 13099
  • 14 Kumar GS, Kapur M. Org. Lett. 2016; 18: 1112
  • 15 Mishra NK, Choi M, Jo H, Oh Y, Sharma S, Han SH, Jeong T, Han S, Lee S.-Y, Kim IS. Chem. Commun. 2015; 51: 17229
  • 16 Lee H, Yi CS. Organometallics 2016; 35: 1973