Nano-Pd/Al(OH)₃-Catalyzed Suzuki–Miyaura Coupling Reaction of Potassium Aryl- and Heteroaryltrifluoroborates with Electrophiles in Alcohols

Abstract

Highly active aluminium hydroxide supported nanopalladium-catalyzed Suzuki–Miyaura coupling reactions of potassium aryl- and heteroaryltrifluoroborates with aryldiazonium salts or aromatic, heteroaromatic halides have been achieved, respectively. Most substrates were shown to cross-couple with ease to aryl compounds as well as to a variety of heteroaromatic bromides in good to excellent yields.

Key words

Pd/Al(OH)₃ - Suzuki–Miyaura - potassium aryltrifluoroborates - aryldiazonium tetrafluoroborate salts - aryl halides

• References and Notes


For recent reviews on the coupling reactions with organoboron compounds, see:
• 1a Miyaura N, Suzuki A. Chem. Rev. 1995; 95: 2457
• 1b Suzuki A In Metal-Catalyzed Cross-Coupling Reactions. Diederich F, Stang PJ. Wiley-VCH; Weinheim: 1998: 49-97
• 1c Molander GA, Ellis N. Acc. Chem. Res. 2007; 40: 275
• 1d Jana R, Pathak TP, Sigman MS. Chem. Rev. 2011; 111: 1417
• 1e Magano J, Dunetz JR. Chem. Rev. 2011; 111: 2177
• 1f Molander GA, Canturk B. Angew. Chem. Int. Ed. 2009; 48: 9240
• 1g Suzuki A. Angew. Chem. Int. Ed. 2011; 50: 6723

For recent selected examples, see:
• 2a Sengupta S, Bhattacharyya S. J. Org. Chem. 1997; 62: 3405
• 2b Suzuki A. J. Organomet. Chem. 1999; 576: 147
• 2c Quach TD, Batey RA. Org. Lett. 2003; 5: 4397
• 2d Fang G.-H, Yan Z.-J, Deng M.-Z. Org. Lett. 2004; 6: 357
• 2e Molander GA, Fumagalli T. J. Org. Chem. 2006; 71: 5743
• 2f Molander GA, Sandrock DL. Org. Lett. 2007; 9: 1597
• 2g Dreher SD, Dormer PG, Sandrock DL, Molander GA. J. Am. Chem. Soc. 2008; 130: 9257
• 2h Dreher SD, Lim SE, Sandrock DL, Molander GA. J. Org. Chem. 2009; 74: 3626
• 2i Molander GA, Gormisky PE, Sandrock DL. J. Org. Chem. 2008; 73: 2052
• 2j Molander GA, Vargas F. Org. Lett. 2007; 9: 203

For selected Cu-catalyzed reactions, see:
• 3a Quach TD, Batey RA. Org. Lett. 2003; 5: 1381
• 3b Bolshan Y, Batey RA. Angew. Chem. Int. Ed. 2008; 47: 2109
• 3c Gurung SK, Thapa S, Kafle A, Dickie DA, Giri R. Org. Lett. 2014; 16: 1264

For selected Ni-catalyzed reactions, see:
• 3d Molander GA, Argintaru OA, Aron I, Dreher SD. Org. Lett. 2010; 12: 5783
• 3e Zhang N, Hoffman DJ, Gutsche N, Gupta J, Percec V. J. Org. Chem. 2012; 77: 5956

For selected Rh-catalyzed reactions, see:
• 3f Luo Y, Hepburn HB, Chotsaeng N, Lam HW. Angew. Chem. Int. Ed. 2012; 51: 8309

For selected Pd-catalyzed reactions, see:
• 3g Zhang C, Huang J, Trudell ML, Nolan SP. J. Org. Chem. 1999; 64: 3804
• 3h Molander GA, Biolatto B. Org. Lett. 2002; 4: 1867
• 3i Navarro O, Kelly RA. III, Nolan SP. J. Am. Chem. Soc. 2003; 125: 16194
• 3j Molander GA, Elia MD. J. Org. Chem. 2006; 71: 9198

For selected Fe-promoted reactions, see:
• 3k Wen J, Qin S, Ma L.-F, Dong L, Zhang J, Liu S.-S, Duan Y.-S, Chen S.-Y, Hu C.-W, Yu X.-Q. Org. Lett. 2010; 12: 2694

For selected Au-catalyzed reaction, see:
• 3l Han J, Liu Y, Guo R. J. Am. Chem. Soc. 2009; 131: 2060
• 4 For recent reviews about complex-catalyzed reactions, see ref. 1f and: Dupont J, Consorti CS, Spencer J. Chem. Rev. 2005; 105: 2527

For recent selected Pd complex catalyzed examples, see ref. 2f and:
• 5a Andrus MB, Song C. Org. Lett. 2001; 3: 3761
• 5b Dubbaka SR, Vogel P. Org. Lett. 2004; 6: 95
• 5c Barder TE, Buchwald SL. Org. Lett. 2004; 6: 2649
• 5d Molander GA, Petrillo DE, Landzberg NR, Rohanna JC, Biolatto B. Synlett 2005; 1763
• 5e Molander GA, Brown AR. J. Org. Chem. 2006; 71: 9681
• 5f Molander GA, Jean-Gérard L. J. Org. Chem. 2009; 74: 1297
• 5g Molander GA, Jean-Gérard L. J. Org. Chem. 2009; 74: 5446
• 5h Molander GA, Canturk B, Kennedy LE. J. Org. Chem. 2009; 74: 973
• 5i Kim D.-S, Ham J. Org. Lett. 2010; 12: 1092
• 5j Chow WK, So CM, Lau CP, Kwong FY. J. Org. Chem. 2010; 75: 5109
• 5k Colombel V, Rombouts F, Oehlrich D, Molander GA. J. Org. Chem. 2012; 77: 2966
• 5l Wong SM, So CM, Chung KH, Luk CH, Lau CP, Kwong FY. Tetrahedron Lett. 2012; 53: 3754
• 5m Molander GA, Wisniewski SR. J. Am. Chem. Soc. 2012; 134: 16856
• 5n Yuen OY, Wong SM, Chan KF, So CM, Kwong FY. Synthesis 2014; 46: 2826
• 5o Xiao Y.-L, Zhang B, Feng Z, Zhang X.-G. Org. Lett. 2014; 16: 4822
• 5p Molander GA, Rivero MR. Org. Lett. 2002; 4: 107
• 5q Molander GA, Gormisky PE. J. Org. Chem. 2008; 73: 7481

For recent reviews about palladium nanoparticle catalyzed reactions, see:
• 6a Yin L, Liebscher J. Chem. Rev. 2007; 107: 133
• 6b Fihri A, Bouhrara M, Nekoueishahraki B, Basset J.-M, Polshettiwar V. Chem. Rev. Soc. 2011; 40: 5181
• 6c Shi JL. Chem. Rev. 2013; 113: 2139
• 7a Garrett CE, Prasad K. Adv. Synth. Catal. 2004; 346: 889
• 7b Lu F, Ruiz J, Astruc D. Tetrahedron Lett. 2004; 45: 9443
• 7c Wang L, Li P.-H. Chin. J. Chem. 2006; 24: 770
• 7d Masllorens J, González I, Roglans A. Eur. J. Org. Chem. 2007; 158
• 7e Jin M.-J, Lee D.-H. Angew. Chem. Int. Ed. 2010; 49: 1119
• 8 Molnár A. Chem. Rev. 2011; 111: 2251

For recent selected examples, see:
• 9a Herrmann WA, Reisinger C.-P, Spiegler M. J. Organomet. Chem. 1998; 557: 93
• 9b Zhang C, Trudell ML. Tetrahedron Lett. 2000; 41: 595
• 9c Wu L, Li B.-L, Huang Y.-Y, Zhou H.-F, He Y.-M, Fan Q.-H. Org. Lett. 2006; 8: 3605
• 9d Kovala-Demertzi D, Kourkoumelis N, Derlat K, Michalak J, Andreadaki FJ, Kostas ID. Inorg. Chim. Acta 2008; 361: 1562
• 10 Darses S, Genet J.-P. Chem. Rev. 2008; 108: 288

For recent reviews and selected examples on the coupling reactions with RBF₃K salts, see ref. 3h and:
• 11a Molander GA, Yun C.-S, Ribagorda M, Biolatto B. J. Org. Chem. 2003; 68: 5534
• 11b Darses S, Genet J.-P. Eur. J. Org. Chem. 2003; 4313
• 11c Kabalka GW, Al-Masum M. Tetrahedron Lett. 2005; 46: 6329
• 11d Cella R, Cunha RL. O. R, Reis AE. S, Pimenta DC, Klitzke CF, Stefani HA. J. Org. Chem. 2006; 71: 244
• 11e Wu J, Zhang L, Xia H.-G. Tetrahedron Lett. 2006; 47: 1525
• 11f Wu J, Zhang L, Luo Y. Tetrahedron Lett. 2006; 47: 6747
• 11g Arvela RK, Leadbeater NE, Mack TL, Kormos CM. Tetrahedron Lett. 2006; 47: 217
• 11h Kabalka GW, Zhou L.-L, Naravane A. Tetrahedron Lett. 2006; 47: 6887
• 11i Zhang L, Meng T, Wu J. J. Org. Chem. 2007; 72: 9346
• 11j Huang H, Jia K, Chen Y. Angew. Chem. Int. Ed. 2015; 54: 1881

For recent selected examples, see ref. 11g and:
• 12a Molander GA, Biolatto B. J. Org. Chem. 2003; 68: 4302
• 12b LeBlond CR, Butler KM, Ferrington MW, Browe MA. Synth. Commun. 2009; 39: 636
• 12c Zhao J.-L, Zhang Y.-H, Cheng K. J. Org. Chem. 2008; 73: 7428
• 12d Kuriyama M, Shimazawa R, Enomoto T, Shirai R. J. Org. Chem. 2008; 73: 6939
• 12e Harker RL, Crouch RD. Synthesis 2007; 25
• 12f Ren W, Li J, Zou D, Wu Y, Wu Y. Tetrahedron 2012; 68: 1351
• 12g Liu LF, Dong Y, Pang B, Ma JH. J. Org. Chem. 2014; 79: 7193
• 12h Batey RA, Quach TD. Tetrahedron Lett. 2001; 42: 9099
• 12i Alacid E, Nájera C. Org. Lett. 2008; 10: 5011
• 12j Vieria AS, Cunha RL, Klitzke CF, Zukerman-Schpector J, Stefani HA. Tetrahedron 2010; 66: 773
• 12k Civivos JF, Gholinejad M, Alonso DA, Nájera C. Chem. Lett. 2011; 40: 907
• 12l Masuyama Y, Sugioka Y, Chonan S, Suzuki N, Fujita M, Hara K, Fukuoka A. J. Mol. Catal. A: Chem. 2012; 352: 81
• 12m Gallo V, Mastrorilli P, Nobile CF, Paolillo R, Taccardi N. Eur. J. Inorg. Chem. 2005; 582
• 12n Liu L, Dong Y, Tang N. Green Chem. 2014; 16: 2185
• 12o Joliton A, Carreira EM. Org. Lett. 2013; 15: 5147
• 12p Colombel V, Presset M, Oehlrich D, Rombouts F, Molander GA. Org. Lett. 2012; 14: 1680
• 12q Tan J.-J, Chen Y.-G, Li H.-M, Yasuda N. J. Org. Chem. 2014; 79: 8871
• 13a Cacchi S, Caponetti E, Casadei MA, Giulio AD, Fabrizi G, Forte G, Goggiamani A, Moreno S, Paolicelli P, Petrucci F. Green Chem. 2012; 14: 317
• 13b Gómez-Martínez M, Buxaderas E, Pastor IM, Alonso DA. J. Mol. Catal. A: Chem. 2015; 404: 1
• 14a Li X, Yan X.-Y, Chang H.-H, Wang L.-C, Zhang Y, Chen W.-W, Li Y.-W, Wei W.-L. Org. Biomol. Chem. 2012; 10: 495
• 14b Li X, Wang L.-C, Chang H.-H, Zhang C.-X, Wei W.-L. Appl. Catal. A: Gen. 2013; 462-463: 15
• 15 Kwon MS, Kim N, Park CM, Lee JS, Kang KY, Park J. Org. Lett. 2005; 7: 1077
• 16 The optimal reaction conditions are as follows: Pd catalyst (0.1 mol%) and stirring for 6 h at 25 °C in MeOH (1.0 mL).
• 17 General Procedure for Suzuki–Miyaura Coupling of 4-Bromobenzenediazonium Tetrafluoroborate Salt with Potassium Phenyltrifluoroborate: To a tube equipped with a magnetic stir bar were added the Pd catalyst 1 (4.8 mg, 0.1 mol% Pd), 4-bromobenzenediazonium tetrafluoroborate salt 1a (0.2 mmol) and potassium phenyltrifluoroborate 2a (1.1 equiv, 0.22 mmol) in turn. Subsequently, the solvent (MeOH, 1.0 mL) was added under air atmosphere. The reaction system was then stirred at r.t. until the substrate was completely consumed as determined by TLC. The reaction mixture was purified by silica gel column chromatography to afford the desired pure coupling product 4b
• 18 Extensive screening showed that the optimized reaction conditions were 0.2-mmol scale of 2a with 3a (1.1 equiv) in the presence of KOAc (4.0 equiv) under air atmosphere in 0.5 mL of PEG-200 at 90 °C.
• 19 General Procedure for Suzuki–Miyaura Coupling Reactions of 4-Methoxybromobenzene with Potassium Phenyltrifluoroborate: To a tube equipped with a magnetic stir bar were added the Pd catalyst 1 (8.7 mg, 0.18 mol% Pd), KOAc (4.0 equiv, 78.4 mg, 0.8 mmol), potassium phenyltrifluoroborate 2a (0.2 mmol) and 4-methoxybromobenzene 3a (1.1 equiv, 0.22 mmol) in turn. Subsequently, the solvent (PEG-200, 1.0 mL) was added under air atmosphere. The reaction system was then heated to 90 °C and stirred until the substrate was completely consumed as determined by TLC. The reaction mixture was purified by silica gel column chromatography to afford the desired pure coupling product 4l.