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Arylboronic acids as versatile coupling partners in fast microwave promoted oxidative Heck chemistry

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Abstract

The useful and selective reactivity of arylboronic acids makes them favourite building blocks for many modern organic chemistry applications like the metal‐mediated formation of C–C, C–O, C–N, and C–S bonds. This report describes oxidative Heck coupling reactions of arylboronic acids and olefins, which were conveniently and rapidly (5–30 min) carried out under air with temperature‐controlled microwave heating. Different reaction conditions were investigated with regard to both microwave heating capability and chemical productivity. Copper(II) acetate was identified as a microwave compatible reoxidant of Pd(0). The scope and limitations of this high‐speed chemistry protocolwith diverse olefins and organoboronic acids are discussed.

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References

  1. Heck, R. F., Palladium‐catalyzed reactions of organic halideswith olefins, Acc. Chem. Res., 12 (1979) 146–151.

    Google Scholar 

  2. Larhed, M. and Hallberg, A., ‘The Heck Reaction (Alkene Substitution via Carbopalladation‐dehydropalladation) and Related Carbopalladation Reactions’, in E. Negishi (ed.), tiHandbook of Organopalladium Chemistry for Organic Synthesis, 1, 2002, pp. 1133–1178.

  3. Lorsbach, B. A. and Kurth, M. J., Carbon‐carbon bond forming solid‐phase reactions, Chem. Rev., 99 (1999) 1549–1581.

    Google Scholar 

  4. Shibasaki, M. and Miyazaki, F., ‘Asymmetric Heck Reactions’, in E. Negishi (ed.), tiHandbook of Organopalladium Chemistry for Organic Synthesis, 1, 2002, pp. 1283–1315.

  5. Whitcombe, N. J., Hii, K. K. and Gibson, S. E., Advances in the Heck chemistry of aryl bromides and chlorides, Tetrahedron, 57 (2001) 7449–7476.

    Google Scholar 

  6. Miyaura, N. and Suzuki, A., Palladium‐catalyzed crosscoupling reactions of organoboron compounds, Chem. Rev., 95 (1995) 2457–2483.

    Google Scholar 

  7. Chemler, S. R., Trauner, D. and Danishefsky, S. J., The β‐alkyl Suzuki‐Miyaura cross‐coupling reaction: Development, mechanistic study, and applications in natural product synthesis, Angew. Chem., Int. Ed., 40 (2001) 4544–4568.

    Google Scholar 

  8. Suzuki, A., Cross‐coupling reactions via organoboranes, J. Organomet. Chem., 653 (2002) 83–90.

    Google Scholar 

  9. Kotha, S., Lahiri, K. and Kashinath, D., Recent applications of the Suzuki‐Miyaura cross‐coupling reaction in organic synthesis, Tetrahedron, 58 (2002) 9633–9695.

    Google Scholar 

  10. Dieck, H. A. and Heck, R. F., Palladium‐catalyzed conjugated diene synthesis from vinylic halides and olefinic compounds, J. Org. Chem., 40 (1975) 1083–1090.

    Google Scholar 

  11. Cho, C. S. and Uemura, S., Palladium‐catalyzed crosscoupling of aryl and alkenyl boronic acids with alkenes via oxidative addition of a carbon–boron bond to palladium(0), J. Organomet. Chem., 465 (1994) 85–92.

    Google Scholar 

  12. Du, X., Suguro, M., Hirabayashi, K., Mori, A., Nishikata, T., Hagiwara, N., Kawata, K., Okeda, T., Wang, H. F., Fugami, K. and Kosugi, M., Mizoroki‐Heck type reaction of organoboron reagents with alkenes and alkynes. A Pd(II)‐catalyzed pathway with Cu(OAc) in2 as an oxidant, Org. Lett., 3 (2001) 3313–3316.

    Google Scholar 

  13. Lautens, M., Roy, A., Fukuoka, K., Fagnou, K. and Martin‐Matute, B., Rhodium‐catalyzed coupling reactions of arylboronic acids to olefins in aqueous media, J. Am. Chem. Soc., 123 (2001) 5358–5359.

    Google Scholar 

  14. Available Chemical Directory, ISIS Base, MDL Information Systems Inc., San Leandro, CA, U.S.A.

  15. Cho, J.‐Y., Tse, M. K., Holmes, D., Maleczka Jr., R. E. and Smith III, M. R., Remarkably selective iridium catalysts for the elaboration of aromatic C–H bonds, Science, 295 (2002) 305–308.

    Google Scholar 

  16. Ishiyama, T., Takagi, J., Ishida, K., Miyaura, N., Anastasi, N. R. and Hartwig, J. F., Mild iridium‐catalyzed borylation of arenes. High turnover numbers, room temperature reactions, and isolation of a potential intermediate, J. Am. Chem. Soc., 124 (2002) 390–391.

    Google Scholar 

  17. Ishiyama, T., Takagi, J., Hartwig, J. F. and Miyaura, N., A stoichiometric aromatic C–H borylation catalyzed by iridium(I)/2,2'‐bipyridine complexes at room temperature, Angew. Chem., Int. Ed., 41 (2002) 3056–3058.

    Google Scholar 

  18. Fagnou, K. and Lautens, M., Rhodium‐catalyzed carbon–carbon bond forming reactions of organometallic compounds, Chem. Rev., 103 (2003) 169–196.

    Google Scholar 

  19. Lautens, M., Fagnou, K. and Hiebert, S., Transition metalcatalyzed enantioselective ring‐opening reactions of oxabicyclic alkenes, Acc. Chem. Res., 36 (2003) 48–58.

    Google Scholar 

  20. Farrington, E. J., Brown, J. M., Barnard, C. F. J. and Roswell, E., Ruthenium‐catalyzed oxidative Heck reactions, Angew. Chem., Int. Ed., 41 (2002) 169–171.

    Google Scholar 

  21. Koike, T., Du, X., Sanada, T., Danda, Y. and Mori, A., Iridium‐catalyzed Mizoroki‐Heck‐type reaction of organosilicon reagents, Angew. Chem., Int. Ed., 42 (2003) 89–92.

    Google Scholar 

  22. Larhed, M. and Hallberg, A., Microwave‐assisted high‐speed chemistry: A new technique in drug discovery, Drug Discovery Today, 6 (2001) 406–416.

    Google Scholar 

  23. Larhed, M., Moberg, C. and Hallberg, A., Microwave‐accelerated homogeneous catalysis in organic chemistry, Acc. Chem. Res, 35 (2002) 717–727.

    Google Scholar 

  24. Kappe, C. O., High‐speed combinatorial synthesis utilizing microwave irradiation, Curr. Opin. Chem. Biol., 6 (2002) 314–320.

    Google Scholar 

  25. Moreno‐Mañas, M., Perez, M. and Pleixats, R., Palladium‐catalyzed Suzuki‐type self‐coupling of arylboronic acids. A mechanistic study, J. Org. Chem., 61 (1996) 2346–2351.

    Google Scholar 

  26. Parrish, J. P., Flanders, V. L., Floyd, R. J. and Jung, K. W., Mild and efficient formation of symmetric biaryls via Pd(II) catalysts and Cu(II) oxidants, Tetrahedron Lett., 42 (2001) 7729–7731.

    Google Scholar 

  27. Leadbeater, N. E. and Marco, M., Rapid and amenable suzuki coupling reaction in water using microwave and conventional heating, J. Org. Chem., 68 (2003) 888–892.

    Google Scholar 

  28. Lam, P. Y. S., Vincent, G., Clark, C. G., Deudon, S. and Jadhav, P. K., Copper‐catalyzed general C–N and C–O bond cross‐coupling with arylboronic acid, Tetrahedron Lett., 42 (2001) 3415–3418.

    Google Scholar 

  29. Simon, J., Salzbrunn, S., Prakash, G. K. S., Petasis, N. A. and Olah, G. A., Regioselective conversion of arylboronic acids to phenols and subsequent coupling to symmetrical diaryl ethers, J. Org. Chem., 66 (2001) 633–634.

    Google Scholar 

  30. Whittaker, A. G. and Mingos, D. M. P., Arcing and other microwave characteristics of metal powders in liquid systems, J. Chem. Soc. Dalton Trans., (2000) 15210–1526.

  31. Whittaker, A. G. and Mingos, D. M. P., Synthetic reactions using metal powders under microwave irradiation, J. Chem. Soc. Dalton Trans., (2002) 3967–3970.

  32. Inoue, A., Shinokubo, H. and Oshima, K., Oxidative Hecktype reaction involving cleavage of a carbon‐phosphorus bond of arylphosphonic acids, J. Am. Chem. Soc., 125 (2003) 1484–1485.

    Google Scholar 

  33. Myers, A. G., Tanaka, D. and Mannion, M. R., Development of a decarboxylative palladation reaction and its use in a Hecktype olefination of arene carboxylates, J. Am. Chem. Soc., 124 (2002) 11250–11251.

    Google Scholar 

  34. Kratsmar‐Smogrovic, J., Svajlenova, O. and Kohutova, M., Copper(II) complexes with organic ligands. XVIII. Magnetic and spectral properties of cresotatocopper(II) complexes with pyridine, Chemicke Zvesti, 29 (1975) 721–726.

    Google Scholar 

  35. Lenarcik, B., Rzepka, M. and Glowacki, J., Stability and structure of cobalt(II), nickel(II), copper(II), zinc(II), and cadmium(II) complexes of pyridine derivatives. Part VI. Comparison of donor properties of alkylpyridines, Pol. J. Chem., 53 (1979) 2199–2208.

    Google Scholar 

  36. Kaiser, N. F. K., Bremberg, U., Larhed, M., Moberg, C. and Hallberg, A., Fast, convenient, and efficient molybdenumcatalyzed asymmetric allylic alkylation under noninert conditions: An example of microwave‐promoted fast chemistry, Angew. Chem., Int. Ed., 39 (2000) 3596–3598.

    Google Scholar 

  37. Luo, Z., Zhang, Q., Oderaotoshi, Y. and Curran, D. P., Fluorous mixture synthesis: A fluorous‐tagging strategy for the synthesis and separation of mixtures of organic compounds, Science, 291 (2001) 1766–1769.

    Google Scholar 

  38. Gladysz, J. A., Curran, D. P. and Editors, 2002: Fluorous chemistry: Tetrahedron symposium‐in‐print number 91 (in: Tetrahedron, 58 (2002)), 308 p.

  39. Zhang, W., Fluorous technologies for solution‐phase highthroughput organic synthesis, Tetrahedron, 59 (2003) 4475–4489.

    Google Scholar 

  40. Darses, S., Pucheault, M. and Genet, J.‐P., Efficient access to perfluoroalkylated aryl compounds by Heck reaction, Eur. J. Org. Chem., (2001) 1121–1128.

  41. Chen, W., Xu, L. and Xiao, J., A general method to fluorous ponytail‐substituted aromatics, Tetrahedron Lett., 42 (2001) 4275–4278.

    Google Scholar 

  42. Cai, M.‐Z., Zhou, J., Zhao, H. and Song, C.‐S., Heck arylation of conjugated alkenes catalyzed by a silica‐supported polyg‐methylselenopropylsiloxane palladium(0) complex, the first polymeric organoselenium palladium complex, J.Chem. Res., Synop. (2002) 76–78.

  43. Gordon, R. S. and Holmes, A. B., Palladium‐mediated crosscoupling reactions with supported reagents in supercritical carbon dioxide, Chem. Comm. (2002) 640–641.

  44. Edwards, M. L., Ritter, H. W., Stemerick, D. M. and Stewart, K. T., Mannich bases of 4‐phenyl‐3‐buten‐2‐one. A new class of antiherpes agent, J. Med. Chem., 26 (1983) 431–436.

    Google Scholar 

  45. Feuerstein, M., Doucet, H. and Santelli, M., Palladium/tetraphosphine catalyzed Heck reaction with orthosubstituted aryl bromides, Synlett, (2001) 1980–1982.

  46. Munoz, M. P., Martin‐Matute, B., Fernandez‐Rivas, C., Cardenas, D. J., and Echavarren, A. M., Palladacycles as precatalysts in Heck and cross‐coupling reactions, Adv. Synth. Catal., 343 (2001) 338–342.

    Google Scholar 

  47. Feuerstein, M., Doucet, H. and Santelli, M., Efficient Heck vinylation of aryl halides catalyzed by a new air‐stable palladium‐tetraphosphine complex, J. Org. Chem., 66 (2001) 5923–5925.

    Google Scholar 

  48. Pereira, M. M., Muller, G., Ordinas, J. I., Azenha, M.E. and Arnaut, L. G., Synthesis of vinylated 5,10,15,20‐tetraphenylporphyrins via Heck‐type coupling reaction and their photophysical properties, J. Chem. Soc., Perkin Trans. 2, (2002) 1583–1588.

    Google Scholar 

  49. Kiuchi, F., Nakamura, N., Tsuda, Y., Kondo, K. and Yoshimura, H., Studies on crude drugs effective on visceral larva migrans. Ii. Larvicidal principles in kaempferiae rhizoma, Chem. Pharm. Bull., 36 (1988) 412–415.

    Google Scholar 

  50. Herrmann, W. A., Elison, M., Fischer, J., Koecher, C. and Artus, G. R. J., Coordination chemistry and mechanisms of metal‐catalyzed C–C coupling reactions. 9. Metal complexes of N‐heterocyclic carbenes – A new structural principle for catalysts in homogeneous catalysis, Angew. Chem., Int. Ed., 34 (1995) 2371–2374.

    Google Scholar 

  51. Yasuda, M., Isami, T., Kubo, J., Mizutani, M., Yamashita, T. and Shima, K., Regiochemistry on photoamination of stilbene derivatives with ammonia via electron transfer, J. Org. Chem., 57 (1992) 1351–1354.

    Google Scholar 

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Authors and Affiliations

  1. Department of Medicinal Chemistry, Organic Pharmaceutical Chemistry, Biomedical Centre, Uppsala University, Uppsala, Sweden

    Murugaiah M. S. Andappan, Peter Nilsson & Mats Larhed

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  1. Murugaiah M. S. Andappan
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  2. Peter Nilsson
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  3. Mats Larhed
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Correspondence to Mats Larhed.

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Andappan, M.M.S., Nilsson, P. & Larhed, M. Arylboronic acids as versatile coupling partners in fast microwave promoted oxidative Heck chemistry. Mol Divers 7, 97–106 (2003). https://doi.org/10.1023/B:MODI.0000006803.99656.8c

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