A Highly Stereoselective Optical Switching Process Based on Donor–Acceptor Substituted Dissymmetric Alkenes
1995; Wiley; Volume: 34; Issue: 3 Linguagem: Inglês
10.1002/anie.199503481
ISSN1521-3773
AutoresWolter F. Jager, Johannes C. de Jong, Ben de Lange, Nina P. M. Huck, Auke Meetsma, Ben L. Feringa,
Tópico(s)Porphyrin and Phthalocyanine Chemistry
ResumoAngewandte Chemie International Edition in EnglishVolume 34, Issue 3 p. 348-350 Communication A Highly Stereoselective Optical Switching Process Based on Donor–Acceptor Substituted Dissymmetric Alkenes† Dr. Wolter F. Jager, Dr. Wolter F. Jager Department of Organic and Molecular Inorganic Chemistry Groningen Centre for Catalysis and Synthesis University of Groningen Nyenborgh 4, NL-9747 AG Groningen (The Netherlands) Telefax: Int. code + (50)634296Search for more papers by this authorDr. Johannes C. de Jong, Dr. Johannes C. de Jong Department of Organic and Molecular Inorganic Chemistry Groningen Centre for Catalysis and Synthesis University of Groningen Nyenborgh 4, NL-9747 AG Groningen (The Netherlands) Telefax: Int. code + (50)634296Search for more papers by this authorDr. Ben de Lange, Dr. Ben de Lange Department of Organic and Molecular Inorganic Chemistry Groningen Centre for Catalysis and Synthesis University of Groningen Nyenborgh 4, NL-9747 AG Groningen (The Netherlands) Telefax: Int. code + (50)634296Search for more papers by this authorDrs. Nina P. M. Huck, Drs. Nina P. M. Huck Department of Organic and Molecular Inorganic Chemistry Groningen Centre for Catalysis and Synthesis University of Groningen Nyenborgh 4, NL-9747 AG Groningen (The Netherlands) Telefax: Int. code + (50)634296Search for more papers by this authorDrs. Auke Meetsma, Drs. Auke Meetsma Department of Organic and Molecular Inorganic Chemistry Groningen Centre for Catalysis and Synthesis University of Groningen Nyenborgh 4, NL-9747 AG Groningen (The Netherlands) Telefax: Int. code + (50)634296Search for more papers by this authorProf. Dr. Ben L. Feringa, Corresponding Author Prof. Dr. Ben L. Feringa Department of Organic and Molecular Inorganic Chemistry Groningen Centre for Catalysis and Synthesis University of Groningen Nyenborgh 4, NL-9747 AG Groningen (The Netherlands) Telefax: Int. code + (50)634296Department of Organic and Molecular Inorganic Chemistry Groningen Centre for Catalysis and Synthesis University of Groningen Nyenborgh 4, NL-9747 AG Groningen (The Netherlands) Telefax: Int. code + (50)634296Search for more papers by this author Dr. Wolter F. Jager, Dr. Wolter F. Jager Department of Organic and Molecular Inorganic Chemistry Groningen Centre for Catalysis and Synthesis University of Groningen Nyenborgh 4, NL-9747 AG Groningen (The Netherlands) Telefax: Int. code + (50)634296Search for more papers by this authorDr. Johannes C. de Jong, Dr. Johannes C. de Jong Department of Organic and Molecular Inorganic Chemistry Groningen Centre for Catalysis and Synthesis University of Groningen Nyenborgh 4, NL-9747 AG Groningen (The Netherlands) Telefax: Int. code + (50)634296Search for more papers by this authorDr. Ben de Lange, Dr. Ben de Lange Department of Organic and Molecular Inorganic Chemistry Groningen Centre for Catalysis and Synthesis University of Groningen Nyenborgh 4, NL-9747 AG Groningen (The Netherlands) Telefax: Int. code + (50)634296Search for more papers by this authorDrs. Nina P. M. Huck, Drs. Nina P. M. Huck Department of Organic and Molecular Inorganic Chemistry Groningen Centre for Catalysis and Synthesis University of Groningen Nyenborgh 4, NL-9747 AG Groningen (The Netherlands) Telefax: Int. code + (50)634296Search for more papers by this authorDrs. Auke Meetsma, Drs. Auke Meetsma Department of Organic and Molecular Inorganic Chemistry Groningen Centre for Catalysis and Synthesis University of Groningen Nyenborgh 4, NL-9747 AG Groningen (The Netherlands) Telefax: Int. code + (50)634296Search for more papers by this authorProf. Dr. Ben L. Feringa, Corresponding Author Prof. Dr. Ben L. Feringa Department of Organic and Molecular Inorganic Chemistry Groningen Centre for Catalysis and Synthesis University of Groningen Nyenborgh 4, NL-9747 AG Groningen (The Netherlands) Telefax: Int. code + (50)634296Department of Organic and Molecular Inorganic Chemistry Groningen Centre for Catalysis and Synthesis University of Groningen Nyenborgh 4, NL-9747 AG Groningen (The Netherlands) Telefax: Int. code + (50)634296Search for more papers by this author First published: February 21, 1995 https://doi.org/10.1002/anie.199503481Citations: 86 † This investigation was financially supported by the Technology Foundation (STW) and the Dutch Foundation for Scientific Research (NWO), and was carried out in cooperation with Philips Research Laboratories (The Netherlands). AboutPDF 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 reversible photoisomerization of the helical thioxanthenes 1 and 2 leads to photostationary states with large diastereomeric excesses. These compounds are promising starting materials for optical data storage devices. References 1(a) B. L. Feringa, W. F. Jager, B. de Lange, Tetrahedron 1993, 49, 8267; (b) M. Emmelius, G. Pawlowski, H. W. Vollmann, Angew. Chem. 1989, 101, 1475; Angew. Chem. Int. Ed. Engl. 1989, 28, 1445. 2(a) Review: H. Dürr, Angew. Chem. 1989, 101, 427; Angew. Chem. Int. Ed. Engl. 1989, 28, 413; (b) S. H. Kawai, S. L. Gilat, J. M. Lehn, J. Chem. Soc. Chem. Commun. 1994, 1011; (c) Y. Yokoyama, K. Sugiyama, S. Yamada, H. Takimoto, Y. Kurita, Chem. Lett. 1994, 749; (d) I. Cabrera, A. Dittrich, H. Ringsdorf, Angew. Chem. 1991, 103, 106; Angew. Chem. Int. Ed. Engl. 1991, 30, 76. 3 J. H. Wendorff, M. Eich, B. Reck, H. Ringsdorf, Makromol. Chem. Rapid Commun. 1987, 8, 467. 4(a) J. Achatz, C. Fischer, J. Salbeck, J. Daub, J. Chem. Soc. Chem. Commun. 1991, 504; (b) H. Tachibana, R. Azumi, Y. Kawabata, M. Matsumoto, T. Nakamura, Chem. Lett. 1992, 173. 5 B. L. Feringa, W. F. Jager, B. de Lange, E. W. Meijer, J. Am. Chem. Soc. 1991, 113, 5468. 6 The term pseudoenantiomers is used in this context to indicate the opposite helicity of P-3 and M-4. 7(a) D. H. R. Barton, B. J. Willis, J. Chem. Soc. Perkin Trans. 1 1972, 305; (b) R. M. Kellogg, J. Buter, S. Wassenaar, J. Org. Chem. 1972, 37, 4045; (c) A. Schönberg, B. König, E. Singer, Chem. Ber. 1967, 100, 767. 8 Isomers 3 and 4 are readily distinguished by their 1HNMR spectra, as the methyl singlet at δ = 3.07 for 3 (dimethylamino group in the trans position) is shifted upfield to δ = 2.30 for 4 (dimethylamino group in the cis position) owing to the shielding effect of the naphthalene moiety. 9 Further details of the crystal structure investigation may be obtained from the Director of the Cambridge Crystallographic Data Centre, 12 Union Road, GB-Cambridge CB2 1EZ (UK), on quoting the full journal citation. 10 Y. Okamoto, K. Hatada, J. Liq. Chromatogr. 1986, 9, 369. 11(a) W. F. Jager, Chiroptical Molecular Switches: Application of Inherently Dissymmetric Alkenes, Dissertation, Groningen, 1994; (b) W. F. Jager, B. de Lange, A. M. Schoevaars, B. L. Feringa, Tetrahedron: Asymmetry 1993, 4, 1481. 12 For the unsubstituted analogue of 4 (X = S, R1 = R2 = R3 = H, Fig. 1) a racemization barrier of 120.9 ± 0.5 kJ mol−1 was determined, while for the unsubstituted analogue of 1 (X = CH2, R1, R2 = R3 = H, Fig. 1) a racemization barrier of 110.7 ± 0.5 kJ mol−1 was determined (see ref. [11 a]). 13 B. L. Feringa, W. F. Jager, B. de Lange, Tetrahedron Lett. 1992, 33, 2887. 14 In ethanol and chloroform no photostationary state was reached after 30 min irradiation at 300 nm, which implies that the quantum yields for the isomerization processes that occur in these solvents is at least a factor 100 lower than in n-hexane. 15 The isomeric composition of the photostationary state upon irradiation at a wavelength λ is given by: [3]/[4] = ε4Φ4 → 3/ε3Φ3 → 4. 16 E. W. Meijer, B. L. Feringa, Mol. Cryst. Liq. Cryst. 1993, 235, 169. Citing Literature Volume34, Issue3February 21, 1995Pages 348-350 ReferencesRelatedInformation
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