Abstract
In modern high-throughput chemistry, the overall workflow is a crucial factor and much work is devoted to speeding up the process of chemistry development. Since automated microwave-based synthesizers are known to streamline the compound production and to accelerate slow organic transformations, this technology was implemented for Heck reactions with sluggish aryl chlorides. Furthermore, homogeneous palladium-catalyzed Heck vinylations of aryl chlorides can be performed under air under optimized conditions. Based on this finding, controlled microwave heating was utilized to accelerate model reactions down to 30 min employing a mixture of ionic liquid and 1,4-dioxane as solvent.
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Bräse, S., Köbberling, J. and Griebenow, N., Handbook of Organopalladium Chemistry for Organic Synthesis, E.-i. Negishi (ed.), Wiley-Interscience, New York, 2002, Vol. 2, pp. 3117–3131.
Kappe, C. O., High-speed combinatorial synthesis utilizing microwave irradiation, Curr. Opin. Chem. Bio., 6 (2002) 314–320.
Larhed, M. and Hallberg, A., Microwave-assisted high-speed chemistry: A new technique in drug discovery, Drug Discov. Today, 6 (2001) 406–416.
Lidström, P., Tierney, J., Wathey, B. and Westman. J., Microwave assisted organic synthesis – A review, Tetrahedron, 57 (2001) 9225–9283.
Lew, A., Krutzik, P. O., Hart, M. E. and Chamberlin, A. R., Increasing rates of reaction: Microwave-assisted organic synthesis for combinatorial chemistry, J. Comb. Chem., 4 (2002) 95–105.
Larhed, M., Moberg, C. and Hallberg, A., Microwave-accelerated homogeneous catalysis in organic chemistry, Acc. Chem. Res., 35 (2002) 717–727.
Vallin, K. S. A., Emilsson, P., Larhed, M. and Hallberg, A., High-speed Heck reactions in ionic liquid with controlled microwave heating, J. Org. Chem., 67 (2002) 6243–6246.
Littke, A. F. and Fu, G. C., Palladium-catalyzed coupling reactions of aryl chlorides, Angew. Chem. Int. Ed., 41 (2002) 4176–4211.
For the first report of a microwave-heated palladium-catalyzed reaction with an aryl chloride, see: Fürstner, A. and Seidel, G., Microwave-assisted synthesis of pinacol boronates from aryl chlorides catalyzed by a palladium/imidazolium salt system, Org. Lett., 4 (2002) 541–543.
For heterogeneous microwave promoted Heck arylations of aryl chlorides, see: Choudary, M. B., Madhi, S., Chowdari, S. N., Kantam, L. M. and Sreedhar, B., Layered double hydroxide supported nanopalladium catalyst for Heck-, Suzuki-, Sonogashira-, and Stille-type coupling reactions of chloroarenes, J. Am. Chem. Soc., 124 (2002) 14127–14136.
Netherton, M. R. and Fu, G. C., Air-stable trialkylphosphonium salts: simple, practical, and versatile replacements for air-sensitive trialkylphosphines. applications in stoichiometric and catalytic processes, Org. Lett., 3 (2001) 4295–4298.
Heck, R. F., Nolley, J. P., Palladium-catalyzed vinylic hydrogen substitution reactions with aryl, benzyl, and styryl halides, J. Org. Chem., 37 (1972) 2320–2322.
De Meijere, A. and Meyer, F. E., Fine feathers make fine birds: The Heck reaction in modern garb, Angew. Chem. Int. Ed. Engl., 23/24 (1994) 2379–2411.
Beletskaya, I. P. and Cheprakov, A. V., The Heck reaction as a sharpening stone of palladium catalysis, Chem. Rev., 100 (2000) 3009–3066.
Larhed, M. and Hallberg, A., Handbook of Organopalladium Chemistry for Organic Synthesis, E.-i. Negishi (ed.), Wiley-Interscience, New York, 2002, Vol. 1, pp. 1133–1178.
Welton, T., Room-temperature ionic liquids. Solvents for synthesis and catalysis, Chem. Rev., 99 (1999) 2071–2083.
Wasserscheid, P. and Keim, W., Ionic liquids – New ‘solutions’ for transition metal catalysis, Angew. Chem. Int. Ed., 39 (2000) 3773–3789.
Sheldon, R., Catalytic reactions in ionic liquids, Chem. Commun., (2001) 2399–2407.
Ley, S. V., Leach, A. G. and Storer, R. I., A polymer-supported thionating reagent, J. Chem. Soc., Perkin Trans. 1, (2001) 358–361.
Van der Eycken, E., Appukkuttan, P., De Borggraeve, W., Dehaen, W., Dallinger, D. and Kappe, C. O., High-speed microwave-promoted hetero-Diels-Alder reactions of 2(1H)-pyrazinones in ionic liquid doped solvents, J. Org. Chem., 67 (2002) 7904–7907.
Carmichael, A. J., Earle, M. J., Holbrey, J. D., McCormac, P. B. and Seddon, K. R., The Heck reaction in ionic liquids: A multiphasic catalyst system, Org. Lett., 1 (1999) 997–1000.
Selvakumar, K., Zapf, A., Beller, M., New palladium carbene catalysts for the Heck reaction of aryl chlorides in ionic liquids, Org. Lett., 4 (2002) 3031–3033.
Herrmann, W. A., Bohm, V. P.W. and Reisinger, C. P., Application of palladacycles in Heck type reactions, J. Organomet. Chem., 576 (1999) 23–41.
Leadbeater, N. E. and Torenius, H. M., A study of the ionic liquid mediated microwave heating of organic solvents, J.Org. Chem., 67 (2002) 3145–3148.
Herrmann, W. A. and Kocher, C., N-heterocyclic carbenes, Angew. Chem. Int. Ed. Engl., 36 (1997) 2163–2187.
McGuinness, D. S., Cavell, K. J., Skelton, B. W. and White, A. H., Zerovalent palladium and nickel complexes of heterocyclic carbenes: Oxidative addition of organic halides, carbon-carbon coupling processes, and the Heck reaction, Organometallics, 18 (1999) 1596–1605.
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.
Calo, V., Nacci, A., Monopoli, A., Lopez, L. and Di Cosmo, A., Heck reaction of β-substituted acrylates in ionic liquids catalyzed by a Pd-benzothiazole carbene complex, Tetrahedron, 57 (2001) 6071–6077.
Feuerstein, M., Doucet, H. and Santelli, M., Palladium/tetraphosphine catalysed heck reaction with orthosubstituted aryl bromides, Synlett., 12 (2001) 1980–1982.
Montgomery, G. J., McKeown, P., McGown, A. T. and Robins, D. J., Synthesis and antiproliferative activity of unsaturated quinoline derivatives, Anti-Cancer Drug Design, 15 (2000) 171–181.
Dupont, J., Monteiro, A. L., Pozebon, D. and Gruber, S. A., On the use of phosphine-free PdCl 2 (SEt2)2 complex as catalyst precursor for the Heck reaction, Tetrahedron Lett., 42 (2001) 7345–7348.
Beller, M., Hartmut, F., Klaus, K., Reisinger, C. P. and Herrmann, W. A., First palladium-catalyzed Heck reactions with efficient colloidal catalyst systems, J. Organomet. Chem., 520 (1996) 257–259.
Gooben, L. J. and Paetzold, J., Pd-catalyzed decarbonylative olefination of aryl esters: Towards a waste-free Heck reaction, Angew. Chem. Int. Ed., 41 (2002) 1237–1241.
Huddleston, J. G., Willauer, H. D., Swatloski, R. P., Visser, A. E. and Rogers, R. D., Room temperature ionic liquids as novel media for ‘clean’ liquid-liquid extraction, Chem. Commun., (1998) 1765–1766.
Lucas, P., El Mehdi, N., Ho, H. A., Belanger, D. and Breau, L., Expedient synthesis of symmetric aryl ketones and of ambient-temperature molten salts of imidazole, Synthesis, 9 (2000) 1253–1258.
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Datta, G.K., Vallin, K.S.A. & Larhed, M. A rapid microwave protocol for Heck vinylation of aryl chlorides under air. Mol Divers 7, 107–114 (2003). https://doi.org/10.1023/B:MODI.0000006798.53091.a2
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DOI: https://doi.org/10.1023/B:MODI.0000006798.53091.a2