Title: Cavity-Directed, Highly Stereoselective [2+2] Photodimerization of Olefins within Self-Assembled Coordination Cages
Abstract: Angewandte Chemie International EditionVolume 41, Issue 8 p. 1347-1349 Communication Cavity-Directed, Highly Stereoselective [2+2] Photodimerization of Olefins within Self-Assembled Coordination Cages Michito Yoshizawa Dr., Michito Yoshizawa Dr. Department of Applied Chemistry Graduate School of Engineering, Nagoya University, JapanSearch for more papers by this authorYoshihisa Takeyama, Yoshihisa Takeyama Department of Applied Chemistry Graduate School of Engineering, Nagoya University, JapanSearch for more papers by this authorTakahiro Kusukawa Dr., Takahiro Kusukawa Dr. Department of Applied Chemistry Graduate School of Engineering, Nagoya University, JapanSearch for more papers by this authorMakoto Fujita Prof. Dr., Makoto Fujita Prof. Dr. [email protected] CREST, Japan Science and Technology Corporation (JST) Department of Applied Chemistry Graduate School of Engineering, Nagoya University Chikusa-ku, Nagoya 464-8603, Japan, Fax:(+81) 52-789-3199Search for more papers by this author Michito Yoshizawa Dr., Michito Yoshizawa Dr. Department of Applied Chemistry Graduate School of Engineering, Nagoya University, JapanSearch for more papers by this authorYoshihisa Takeyama, Yoshihisa Takeyama Department of Applied Chemistry Graduate School of Engineering, Nagoya University, JapanSearch for more papers by this authorTakahiro Kusukawa Dr., Takahiro Kusukawa Dr. Department of Applied Chemistry Graduate School of Engineering, Nagoya University, JapanSearch for more papers by this authorMakoto Fujita Prof. Dr., Makoto Fujita Prof. Dr. [email protected] CREST, Japan Science and Technology Corporation (JST) Department of Applied Chemistry Graduate School of Engineering, Nagoya University Chikusa-ku, Nagoya 464-8603, Japan, Fax:(+81) 52-789-3199Search for more papers by this author First published: 16 April 2002 https://doi.org/10.1002/1521-3773(20020415)41:8<1347::AID-ANIE1347>3.0.CO;2-XCitations: 298 This work was supported by the Core Research for Evolutional Science and Technology (CREST) project of the Japan Science and Technology Corporation (JST). M.Y. thanks the Japan Society for the Promotion of Science (JSPS) for a fellowship. 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 Graphical Abstract Molecular flasks of self-assembled M6L4 nanocages promote the [2+2] photodimerization of olefins in a surprisingly efficient fashion. Thus, the dimerization of acenaphthylenes and naphthoquinones quantitatively proceeded in the cavity with remarkable rate acceleration and perfect regio- and stereocontrol (>98 %, see scheme). References 1 Recent reviews: 1a D. J. Cram, J. M. Cram, Container Molecules and Their Guests, Royal Society of Chemistry, Cambridge, UK, 1994; 1b M. M. Conn, J. Rebek, Jr., Chem. Rev. 1997, 97, 1647– 1668; 1c A. Jasat, J. C. Sherman, Chem. Rev. 1999, 99, 931– 967; 1d R. Warmuth, J. Yoon, Acc. Chem. Res. 2001, 34, 95– 105; 1e M. Fujita, K. Umemoto, M. Yoshizawa, N. Fujita, T. Kusukawa, K. Biradha, Chem. Commun. 2001, 509– 518. 2 Chemical transformation in self-assembled cage compounds: 2a J. Kang, J. Rebek, Jr., Nature 1997, 385, 50– 52; 2b J. Kang, G. Hilmersson, J. Santameria, J. Rebek, Jr., J. Am. Chem. Soc. 1998, 120, 3650– 3656; 2c J. Kang, J. Santameria, G. Hilmersson, J. Rebek, Jr., J. Am. Chem. Soc. 1998, 120, 7389– 7390; 2d M. Ziegler, J. L. Brumaghim, K. N. Raymond, Angew. Chem. 2000, 112, 4285– 4287; Angew. Chem. Int. Ed. 2000, 39, 4119– 4121; 2e H. Ito, T. Kusukawa, M. Fujita, Chem. Lett. 2000, 598– 599; 2f M. Yoshizawa, T. Kusukawa, M. Fujita, K. Yamaguchi, J. Am. Chem. Soc. 2000, 122, 6311– 6312; 2g M. Yoshizawa, T. Kusukawa, M. Fujita, S. Sakamoto, K. Yamaguchi, J. Am. Chem. Soc. 2001, 123, 10 454– 10 459. 3 L. Pauling, Am. Sci. 1948, 36, 51– 58. 4 4a M. Fujita, D. Oguro, M. Miyazawa, H. Oka, K. Yamaguchi, K. Ogura, Nature 1995, 378, 469– 471; 4b T. Kusukawa, M. Fujita, Angew. Chem. 1998, 100, 3327– 3329; Angew. Chem. Int. Ed. 1998, 37, 3142– 3144; 4c T. Kusukawa, M. Fujita, J. Am. Chem. Soc. 1999, 121, 1397– 1398; 4d T. Kusukawa, M. Yoshizawa, M. Fujita, Angew. Chem. 2001, 113, 1931– 1936; Angew. Chem. Int. Ed. 2001, 40, 1879– 1884; 4e cage 1 is now commercially available from Wako Chemical Co. Ltd. (Pd-Nanocage). 5 5a M. Fujita, S.-Y. Yu, T. Kusukawa, H. Funaki, K. Ogura, K. Yamaguchi, Angew. Chem. 1998, 110, 2192– 2196; Angew. Chem. Int. Ed. 1998, 37, 2082– 2085; 5b S.-Y. Yu, T. Kusukawa, K. Biradha, M. Fujita, J. Am. Chem. Soc. 2000, 122, 2665– 2667. 6 Photochemical reaction within capsules: 6a D. J. Cram, M. E. Tanner, R. Thomas, Angew. Chem. 1991, 103, 1048– 1051; Angew. Chem. Int. Ed. Engl. 1991, 30, 1024– 1028; 6b D. J. Cram, Nature 1992 356, 29– 36; 6c S. Watanabe, K. Goto, T. Kawashima, R. Okazaki, J. Am. Chem. Soc. 1997, 119, 3195– 3196; 6d R. Warmuth, Angew. Chem. 1997, 109, 1406– 1409; Angew. Chem. Int. Ed. 1997, 36, 1347– 1350; 6e R. Warmuth, M. A. Marvel, Angew. Chem. 2000, 112, 1168– 1170; Angew. Chem. Int. Ed. 2000, 39, 1117– 1119; 6f R. Warmuth, M. A. Marvel, Chem. Eur. J. 2001, 7, 1209– 1220; 6g S. Y. Jon, Y. H. Ko, S. H. Park, H-J. Kim, K. Kim, Chem. Commun. 2001, 1938– 1939. 7 Reviews: 7a V. Ramamurthy, Tetrahedron, 1986, 42, 5753– 5839; 7b V. Ramamurthy, K. Venkatesan, Chem. Res. 1987, 87, 433– 481; 7c T. Tamaki, T. Kokubu, K. Ichimura, Tetrahedron 1987, 43, 1485– 1494; 7d V. Ramamurthy, D. F. Eaton, Acc. Chem. Res. 1988, 21, 300– 306. 8 Photodimerization of acenaphthylenes: 8a D. O. Cowan, J. C. Koziar, J. Am. Chem. Soc. 1975, 97, 249– 254; 8b Y. Nakamura, Y. Imakura, T. Kato, Y. Morita, Chem. Commun. 1977, 887– 888; 8c J. M. Nerbonne, R. G. Weiss, J. Am. Chem. Soc. 1978, 100, 2571– 2573; 8d P. Mayo, Pure. Appl. Chem. 1982, 54, 1623– 1632; 8e H. Mayer, J. Sauer, Tetrahedron Lett. 1983, 24, 4091– 4094; 8f V. Ramamurthy, D. R. Corbin, C. V. Kumar, N. J. Turro, Tetrahedron Lett. 1990, 31, 47– 50. 9 Photodimerization of naphthoquinones: 9a J. Rennert, S. Japar, M. Guttman, Photochem. Photobiol. 1967, 6, 485– 490; 9b H. Werbin, E. T. Strom, J. Am. Chem. Soc. 1968, 90, 7296– 7301; 9c J. V. Ellis, J. E. Jones, J. Org. Chem. 1975, 40, 485– 488; 9d F. J. C. Martins, A. M. Viljoen, P. L. Wessels, Tetrahedron 1987, 43, 225– 234. 10 We estimated the yield of dimer to be more than 98 % because a trace amount of the starting material was found in the 1H NMR spectrum. 11 5 a was quantitatively photodissociated to reform 3 a in benzene solution (2 mM) by irradiation for 0.5 h; see for example, R. Livingston, K. S. Wei, J. Phys. Chem. 1967, 71, 541– 547. 12 The 13C-H satellite of the cyclobutane proton at δ=4.02 was observed as a singlet with J=134.7 Hz and corresponds to the product having a head-to-tail conformation. 13 13a P. E. Eaton, J. Am. Chem. Soc. 1962, 84, 2344– 2348; 13b C. S. Foote, Tetrahedron Lett. 1963, 579– 583; 13c R. Anet, Tetrahedron Lett. 1965, 3713– 3717; 13d H. Ziffer, N. E. Sharpless, R. O. Kan, Tetrahedron 1966, 202, 3011–3020; 13e H. Ziffer, J. R. Williams, J. Org. Chem. 1968, 33, 920– 921. Citing Literature Supporting Information Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2002/z18306_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. Volume41, Issue8April 15, 2002Pages 1347-1349 ReferencesRelatedInformation
Publication Year: 2002
Publication Date: 2002-04-15
Language: en
Type: article
Indexed In: ['crossref', 'pubmed']
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