A General Suzuki–Miyaura Coupling of Aryl Chlorides with Potassium Aryltrifluoroborates­ in Water Catalyzed by an Efficient CPCy Phendole-phos–Palladium Complex

Abstract

General examples of the palladium-catalyzed Suzuki–Miyaura cross-coupling of aryl or heteroaryl chlorides with potassium aryl- or heteroaryltrifluoroborates in water are presented. The palladium complex comprising of palladium(II) acetate and ‘CPCy Phendole-phos’ is found to be a highly effective catalyst system for this coupling reaction with low catalyst loading (down to 0.005 mol% Pd).

Key words

palladium - Suzuki–Miyaura reaction - aryl chloride - potassium aryltrifluoroborates - water - arylation

• References

• 1a King AO, Yasuda N In Organometallics in Process Chemistry . Larsen RD. Springer; Berlin: 2004: 205-246
• 1b Miyaura N. Top. Curr. Chem. 2002; 219: 11
• 1c Suzuki A In Modern Arene Chemistry . Astruc D. Wiley-VCH; Weinheim: 2002: 53-106
• 1d Suzuki A. J. Organomet. Chem. 2002; 653: 54
• 1e de Meijere A, Diederich F. Metal-Catalyzed Cross-Coupling Reactions . 2nd ed. Wiley-VCH; Weinheim: 2004: Vols. 1-2
• 2 Hall DG. Boronic Acids . 2nd ed. Wiley-VCH; Weinheim: 2011

For recent reviews on the coupling reactions with R-BF₃K salts, see:
• 3a Molander GA, Canturk B. Angew. Chem. Int. Ed. 2009; 48: 9240
• 3b Molander GA, Ellis NO. Acc. Chem. Res. 2007; 40: 275
• 3c Darses S, Genet J.-P. Chem. Rev. 2008; 108: 288

For selected examples, see:
• 4a Vedejs E, Chapman RW, Fields SC, Lin S, Schrimpf MR. J. Org. Chem. 1995; 60: 3020
• 4b Molander GA, Cooper DJ. J. Org. Chem. 2007; 72: 3558
• 4c Molander GA, Ham J, Canturk B. Org. Lett. 2007; 9: 821

For recent selected examples from Molander’s group, see:
• 5a Molander GA, Shin I. Org. Lett. 2013; 15: 2534
• 5b Molander GA, Shin I. Org. Lett. 2012; 14: 3138
• 5c Molander GA, Fleurt-Brégeot N, Hiebel M.-A. Org. Lett. 2011; 13: 1694
• 5d Molander GA, Hiebel M.-A. Org. Lett. 2010; 12: 4876
• 5e Molander GA, Cavalcanti LN, Canturk B, Pan PS, Kennedy LE. J. Org. Chem. 2009; 74: 7364
• 5f Cho YA, Kim DS, Ahn HR, Canturk B, Molander GA, Ham J. Org. Lett. 2009; 11: 4330
• 5g Molander GA, Febo-Ayala W, Jean-Gérard L. Org. Lett. 2009; 11: 3830
• 5h Molander GA, Jean-Gérard L. J. Org. Chem. 2009; 74: 5446
• 5i Dreher SD, Lim SE, Sandrock DL, Molander GA. J. Org. Chem. 2009; 74: 3626
• 5j Molander GA, Jean-Gérard L. J. Org. Chem. 2009; 74: 1297
• 5k Molander GA, Cooper DJ. J. Org. Chem. 2008; 73: 3885
• 5l Molander GA, Gormisky PE, Sandrock DL. J. Org. Chem. 2008; 73: 2052
• 5m Molander GA, Gormisky PE. J. Org. Chem. 2008; 73: 7481
• 5n Molander GA, Sandrock DL. Org. Lett. 2007; 9: 1597
• 5o Molander GA, Vargas F. Org. Lett. 2007; 9: 203

For recent selected examples, see:
• 6a Abel R, Aggarwal VK. Angew. Chem. Int. Ed. 2009; 48: 6289
• 6b Doucet H. Eur. J. Org. Chem. 2008; 2013
• 6c Kabalka GW, Zhou L.-L, Naravane A. Tetrahedron Lett. 2006; 47: 6887
• 6d Harker RL, Crouch RD. Synthesis 2007; 25
• 6e Wu J, Zhang L, Luo Y. Tetrahedron Lett. 2006; 47: 6747
• 6f Wu J, Zhang L, Xia H.-G. Tetrahedron Lett. 2006; 47: 1525
• 6g Cella R, Cunha RL. O. R, Reis AE. S, Pimenta DC, Klitzke CF, Stefani HA. J. Org. Chem. 2006; 71: 244
• 6h Arvela RK, Leadbeater NE, Mack TL, Kormos CM. Tetrahedron Lett. 2006; 47: 217
• 6i Kabalka GW, Al-Masum M. Tetrahedron Lett. 2005; 46: 6329
• 6j Barder TE, Buchwald SL. Org. Lett. 2004; 6: 2649
• 6k Quach TD, Batey RA. Org. Lett. 2003; 5: 4397
• 6l Quach TD, Batey RA. Org. Lett. 2003; 5: 1381
• 6m Fang G.-H, Yan Z.-J, Deng M.-Z. Org. Lett. 2004; 6: 357
• 6n Darses S, Genet J.-P. Eur. J. Org. Chem. 2003; 4313
• 7a Li C.-J, Chan T.-H. Organic Reactions in Aqueous Media . Wiley-Interscience; New York: 1997
• 7b Cornils B, Herrmann WA. Aqueous-Phase Organometallic Catalysis . 2nd ed. Wiley-VCH; Weinheim: 2004
• 7c Lindström UM. Chem. Rev. 2002; 102: 2751
• 7d Tundo P, Anastas PT. Green Chemistry: Challenging Perspectives . Oxford University Press; Oxford: 2000
• 7e Nelson WM. Green Solvents for Chemistry, Perspective and Practice . Oxford University Press; Oxford: 2003
• 7f Dixneuf PH, Cadierno V. Metal-Catalyzed Reactions in Water . Wiley-VCH; Weinheim: 2013
• 8a Molander GA, Biolatto B. J. Org. Chem. 2003; 68: 4302
• 8b Wang L, Li PH. Chin. J. Chem. 2006; 24: 770
• 9a Alacid E, Nájerra C. Org. Lett. 2008; 10: 5011
• 9b Lysén M, Köhler K. Synthesis 2006; 692
• 10a Kwong FY, Li YM, Lam WH, Qiu L, Lee HW, Yeung CH, Chan KS, Chan AS. C. Chem. Eur. J. 2005; 11: 3872
• 10b So CM, Lau CP, Zhou Z, Kwong FY. Angew. Chem. Int. Ed. 2008; 47: 6402
• 10c Yeung PY, So CM, Lau CP, Kwong FY. Angew. Chem. Int. Ed. 2010; 49: 8918
• 10d Yeung PY, So CM, Lau CP, Kwong FY. Org. Lett. 2011; 13: 648

For phosphine ligand syntheses, see:
• 11a So CM, Lau CP, Kwong FY. Org. Lett. 2007; 9: 2795
• 11b Chen G, Lam WH, Fok WS, Lee HW, Kwong FY. Chem. Asian J. 2007; 2: 306
• 11c So CM, Yeung CC, Lau CP, Kwong FY. J. Org. Chem. 2008; 73: 7803
• 11d So CM, Lau CP, Kwong FY. Angew. Chem. Int. Ed. 2008; 47: 8059
• 11e So CM, Chow WK, Choy PY, Lau CP, Kwong FY. Chem. Eur. J. 2010; 16: 7996
• 11f Chung KH, So CM, Wong SM, Luk CH, Zhou Z, Lau CP, Kwong FY. Chem. Commun. 2012; 48: 1967
• 11g Kwong FY, Chan KS. Chem. Commun. 2000; 1069
• 11h Kwong FY, Lai CW, Tian Y, Chan KS. Tetrahedron Lett. 2000; 41: 10285

For Pd-catalyzed coupling of Ar¹OMs and Ar²BF₃K, see:
• 11i Chow WK, So CM, Lau CP, Kwong FY. J. Org. Chem. 2010; 75: 5109

For reviews, see:
• 11j Wong SM, So CM, Kwong FY. Synlett 2012; 23: 1132
• 11k Kwong FY, Chan AS. C. Synlett 2008; 1440
• 11l So CM, Kwong FY. Chem. Soc. Rev. 2011; 40: 4963
• 12 Lee HW, Lam FL, So CM, Lau CP, Chan AS. C, Kwong FY. Angew. Chem. Int. Ed. 2009; 48: 7436