Studies on the Cocatalyst in Ruthenium-Catalyzed C–H Arylation

Abstract

The performance of three types of Brønsted acid potassium salts, potassium carboxylates, potassium phosphates, and potassium sulfonates, has been tested as the cocatalyst in ruthenium-catalyzed C–H arylation. Among them, dipotassium glutarate, potassium bis(2-ethylhexyl) phosphate, and potassium 2,4,6-trimethylbenzenesulfonate provided higher activity. Potassium 2,4,6-trimethylbenzenesulfonate was the most active even for less reactive substrates, such as electron-deficient azoles and sterically demanding aryl bromides.

Key words

C–H activation - direct arylation - ruthenium - Brønsted acids - biaryls - heterocycles

• References

• 1a Anderson NG In Practical Process Research & Development . Academic Press; Oxford: 2000
• 1b Yasuda N In The Art of Process Chemistry . Wiley-VCH; Weinheim: 2010
• 2 Sheldon RA. Green Chem. 2007; 9: 1273

For example: see,
• 3a Bringmann G, Zagst R, Schäffer M, Hallock YF, Cardellina JH. II, Boyd MR. Angew. Chem., Int. Ed. Engl. 1993; 32: 1190
• 3b Manfredi KP, Blunt JW, Cardellina II JH, McMahon JB. Antibiot. Annu. 1955; 56: 606

For example, see:
• 4a Miyaura N, Suzuki A. Chem. Rev. 1995; 95: 2457
• 4b Negishi E, Anastasia L. Chem. Rev. 2003; 103: 1979
• 5 For example, see: Matheron ME, Porchas M. Plant Dis. 2004; 88: 665
• 6 Trost BM. Science (Washington, D. C.) 1991; 254: 1471
• 7 Murai S, Kakiuchi F, Sekine S, Tanaka Y, Kamatani A, Sonoda M, Chatani N. Nature (London) 1993; 366: 529
• 8a Seki M. WO 2011061996, 2010
• 8b Seki M. ACS Catal. 2011; 1: 607
• 8c Seki M, Nagahama M. J. Org. Chem. 2011; 76: 10198
• 8d Seki M. Synthesis 2012; 44: 3231
• 8e Seki M. J. Synth. Org. Chem. Jpn. 2012; 70: 1295
• 8f This work has been featured: Kocienski P. Synfacts 2013; 9: 0006
• 8g Seki M In Science of Synthesis: Catalytic Transformations via C–H Activation. Yu J.-Q. Thieme; Stuttgart; 2015: in press
• 8h Seki M. WO 2014034868, 2014
• 8i Seki M. WO 2014051008, 2014
• 8j Seki M. RSC Adv. 2014; 4: 29131
• 8k Seki M. Synthesis 2014; 46: 3249
• 8l Seki M. ACS Catal. 2014; 4: 4047
• 9a Daugulis O, Do J.-Q, Shabashov D. Acc. Chem. Res. 2009; 42: 1074
• 9b Chen X, Engle KM, Wang D.-H, Yu J.-Q. Angew. Chem. Int. Ed. 2009; 48: 5094
• 9c Ackermann L, Vicente R, Kapdi AR. Angew. Chem. Int. Ed. 2009; 48: 9792
• 9d Willis MC. Chem. Rev. 2010; 110: 725
• 9e Mkhalid IA. I, Barnard JH, Marder TB, Murphy JM, Hartwig JF. Chem. Rev. 2010; 110: 890
• 9f Ackermann L. Chem. Commun. 2010; 46: 4866
• 9g Dudnik AS, Gevorgyan V. Angew. Chem. Int. Ed. 2010; 49: 2096
• 9h Lyons TW, Sanford MS. Chem. Rev. 2010; 110: 1147
• 9i Sun S.-L, Li B.-J, Shi Z.-J. Chem. Commun. 2010; 46: 677
• 9j Peng HM, Dai L.-X, You S.-L. Angew. Chem. Int. Ed. 2010; 49: 5826
• 9k Ackermann L. Chem. Rev. 2011; 111: 1315
• 9l Arockiam PB, Bruneau C, Dixneuf PH. Chem. Rev. 2012; 112: 5879
• 10a Chiong HA, Pham Q.-N, Daugulis O. J. Am. Chem. Soc. 2007; 129: 9879
• 10b Glri R, Yu J.-Q. J. Am. Chem. Soc. 2008; 130: 14082
• 10c Li M, Ge H. Org. Lett. 2010; 12: 3464
• 10d Potavathri S, Pereira KC, Gorelsky SI, Pike A, LeBris AP, DeBoef B. J. Am. Chem. Soc. 2010; 132: 14676
• 10e Feng Y, Wang Y, Landgraf B, Liu S, Chen G. Org. Lett. 2010; 12: 3414
• 11a Ferrer-Flegeau E, Bruneau C, Dixneuf PH, Jutand A. J. Am. Chem. Soc. 2011; 133: 10161
• 11b Fabre I, von Wolff N, Le Duc G, Ferrer-Flegeau E, Bruneau C, Dixneuf PH, Jutand A. Chem. Eur. J. 2013; 19: 7595
• 12a Pozgan F, Dixneuf PH. Adv. Synth. Catal. 2009; 351: 1737
• 12b Li B, Bheeter CB, Darcel C, Dixneuf PH. ACS Catal. 2011; 1: 1221
• 13 Ouellet SG, Roy A, Molinaro C, Angelaud R, Marcoux JF, O’Shea PD, Davies JW. J. Org. Chem. 2011; 76: 1436
• 14a Arockiam PB, Poirier V, Fischmeister C, Bruneau C, Dixneuf PH. Green Chem. 2009; 11: 1871
• 14b Arockiam PB, Fischmeister C, Bruneau C, Dixneuf PH. Angew. Chem. Int. Ed. 2010; 49: 6629
• 15 Ackermann L, Lygin AV. Org. Lett. 2011; 13: 3332
• 16a Honjo T, Phipps RJ, Rauniyar V, Toste FD. Angew. Chem. Int. Ed. 2012; 51: 9684
• 16b Blażewska KM. J. Org. Chem. 2014; 79: 408
• 17 Liu L, Fu T, Wang T, Gao T, Zeng Z, Zhu J, Zhao Y. J. Org. Chem. 2014; 79: 80
• 18 Hatano M, Maki T, Moriyama K, Arinobe M, Ishihara K. J. Am. Chem. Soc. 2008; 130: 16858