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Brønsted Acid Mediated Heterogeneous Addition Reaction of 1,3‐Dicarbonyl Compounds to Alkenes and Alcohols

2006; Wiley; Volume: 45; Issue: 16 Linguagem: Inglês

10.1002/anie.200504609

1521-3773

Ken Motokura, Noriaki Fujita, Kohsuke Mori, Tomoo Mizugaki, Kohki Ebitani, Kiyotomi Kaneda,

Chemical Synthesis and Reactions

Angewandte Chemie International EditionVolume 45, Issue 16 p. 2605-2609 Communication Brønsted Acid Mediated Heterogeneous Addition Reaction of 1,3-Dicarbonyl Compounds to Alkenes and Alcohols† Ken Motokura Dr., Ken Motokura Dr. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan, Fax: (+81) 6-6850-6260Search for more papers by this authorNoriaki Fujita, Noriaki Fujita Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan, Fax: (+81) 6-6850-6260Search for more papers by this authorKohsuke Mori Dr., Kohsuke Mori Dr. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan, Fax: (+81) 6-6850-6260Search for more papers by this authorTomoo Mizugaki Dr., Tomoo Mizugaki Dr. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan, Fax: (+81) 6-6850-6260Search for more papers by this authorKohki Ebitani Dr., Kohki Ebitani Dr. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan, Fax: (+81) 6-6850-6260Search for more papers by this authorKiyotomi Kaneda Prof. Dr., Kiyotomi Kaneda Prof. Dr. [email protected] Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan, Fax: (+81) 6-6850-6260Search for more papers by this author Ken Motokura Dr., Ken Motokura Dr. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan, Fax: (+81) 6-6850-6260Search for more papers by this authorNoriaki Fujita, Noriaki Fujita Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan, Fax: (+81) 6-6850-6260Search for more papers by this authorKohsuke Mori Dr., Kohsuke Mori Dr. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan, Fax: (+81) 6-6850-6260Search for more papers by this authorTomoo Mizugaki Dr., Tomoo Mizugaki Dr. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan, Fax: (+81) 6-6850-6260Search for more papers by this authorKohki Ebitani Dr., Kohki Ebitani Dr. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan, Fax: (+81) 6-6850-6260Search for more papers by this authorKiyotomi Kaneda Prof. Dr., Kiyotomi Kaneda Prof. Dr. [email protected] Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan, Fax: (+81) 6-6850-6260Search for more papers by this author First published: 04 April 2006 https://doi.org/10.1002/anie.200504609Citations: 131 † This investigation was supported by a Grant-in-Aid for Scientific Research from the Ministry of Education, Culture, Sports, Science, and Technology of Japan (16206078). We thank the Center of Excellence (21COE; "Creation of Integrated Ecochemistry" program, Osaka University). We are also grateful to Prof. Dr. S. Namba (Teikyo University) for catalyst preparation and Dr. K. Mori, Dr. Y. Senga, and Dr. S. Yamakita (Bel Japan) for TPD measurement. K.M. thanks the JSPS for a Research Fellowship for Young Scientists. Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Graphical Abstract The unique acidity of a proton-exchanged montmorillonite catalyst (H-mont) was exploited in the nucleophilic addition of 1,3-dicarbonyl compounds to simple alkenes (see scheme). The benzylation and allylation of 1,3-dicarbonyl compounds with alcohols and nucleophilic addition of carboxylic acids to alkenes also proceeded smoothly with the H-mont catalyst, which could be recovered easily and recycled at least seven times without loss of activity. Supporting Information Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2006/z504609_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article. References 1 1aB. M. 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Soc. 2005, 127, 17184. 5For clay-catalyzed organic synthesis, see: 5aT. J. Pinnavaia, Science 1983, 220, 365; 5bP. Laszlo, Acc. Chem. Res. 1986, 19, 121; 5cY. Izumi, M. Onaka, Adv. Catal. 1992, 38, 245. 6For zeolite catalysis, see: 6aJ. A. Horsley, CHEMTECH 1997, 27, 45; 6bV. Ramamurthy, P. Lakshminarasimhan, C. P. Grey, L. J. Johnston, Chem. Commun. 1998, 2411; 6cC. W. Jones, K. Tsuji, M. E. Davis, Nature 1998, 393, 52; 6dA. Corma, L. T. Nemeth, M. Renz, S. Valencia, Nature 2001, 412, 423. 7For Brønsted acid catalysis, see: 7aK. Ebitani, T. Kawabata, K. Nagashima, T. Mizugaki, K. Kaneda, Green Chem. 2000, 2, 157; 7bK. Motokura, N. Fujita, K. Mori, T. Mizugaki, K. Ebitani, K. Kaneda, J. Am. Chem. Soc. 2005, 127, 9674; for Lewis acid catalysis, see: 7cT. Kawabata, T. Mizugaki, K. Ebitani, K. Kaneda, J. Am. Chem. Soc. 2003, 125, 10486; 7dT. Kawabata, M. Kato, T. Mizugaki, K. Ebitani, K. Kaneda, Chem. Eur. J. 2005, 11, 288. 8 8aM. Niwa, N. Katada, M. Sawa, Y. Murakami, J. Phys. 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Chem. 1998, 63, 3677. 14Benzhydrol is the only alcohol that has been used in previously reported acid-catalyzed benzylation reactions of active methylene groups: 14aF. Bisaro, G. Prestat, M. Vitale, G. Poli, Synlett 2002, 11, 1823; 14bG. C. Gullickson, D. E. Lewis, Aust. J. Chem. 2003, 56, 385. 15The allylation of 1,3-dicarbonyl compounds with allylic alcohols has usually been performed with Pd catalysts, see: 15aX. Lu, X. Jiang, X. Tao, J. Organomet. Chem. 1988, 344, 109; 15bF. Ozawa, H. Okamoto, S. Kawagishi, S. Yamamoto, T. Minami, M. Yoshifuji, J. Am. Chem. Soc. 2002, 124, 10968. 16For the radical addition of active methylene compounds to alkenes, see: K. Hirase, T. Iwahama, S. Sakaguchi, Y. Ishii, J. Org. Chem. 2002, 67, 970. 17For a recent example, see W. Daniell, N.-Y. Topsøe, H. Knözinger, Langmuir 2001, 17, 6233. 18R. G. Person, R. L. Dillon, J. Am. Chem. Soc. 1953, 75, 2439. 19S. M. Alexander, D. M. Bibby, R. F. Howe, R. H. Meinhold, Zeolite 1993, 13, 441. 20For previous examples of two activated substrates at neighboring catalytic sites on solid surfaces, see: 20aK. Yamaguchi, K. Ebitani, T. Yoshida, H. Yoshida, K. Kaneda, J. Am. Chem. Soc. 1999, 121, 4526; 20bT. Seki, H. Tachikawa, T. Yamada, H. Hattori, J. Catal. 2003, 217, 117. Citing Literature Volume45, Issue16April 10, 2006Pages 2605-2609 ReferencesRelatedInformation