cis ‐Bromination of Alkynes without Cationic Intermediates
2005; Wiley; Volume: 44; Issue: 9 Linguagem: Inglês
10.1002/anie.200461632
ISSN1521-3773
AutoresRainer Herges, Andrea Papafilippopoulos, Kirsten Heß, Cinzia Chiappe, Dieter Lenoir, Heiner Detert,
Tópico(s)Oxidative Organic Chemistry Reactions
ResumoAngewandte Chemie International EditionVolume 44, Issue 9 p. 1412-1416 Communication cis-Bromination of Alkynes without Cationic Intermediates† Rainer Herges Prof., Rainer Herges Prof. [email protected] Institut für Organische Chemie, Christian-Albrechts-Universität zu Kiel, Otto-Hahn-Platz 4, 24118 Kiel, Germany, Fax: (+49) 431-880-2440Search for more papers by this authorAndrea Papafilippopoulos Dr., Andrea Papafilippopoulos Dr. Institut für Organische Chemie, Christian-Albrechts-Universität zu Kiel, Otto-Hahn-Platz 4, 24118 Kiel, Germany, Fax: (+49) 431-880-2440Search for more papers by this authorKirsten Hess, Kirsten Hess Institut für Organische Chemie, Christian-Albrechts-Universität zu Kiel, Otto-Hahn-Platz 4, 24118 Kiel, Germany, Fax: (+49) 431-880-2440Search for more papers by this authorCinzia Chiappe Prof., Cinzia Chiappe Prof. Dipartimento di Chimica Bioorganica e Biofarmacia, Università di Pisa, Via Bonanno 33, 56126 Pisa, ItalySearch for more papers by this authorDieter Lenoir Prof., Dieter Lenoir Prof. [email protected] Institut für Ökologische Chemie, GSF-Forschungszentrum für Umwelt und Gesundheit, Postfach 1129, 85778 Neuherberg, Germany, Fax: (+49) 89-3187-3371Search for more papers by this authorHeiner Detert Dr., Heiner Detert Dr. [email protected] Institut für Organische Chemie, Johannes Gutenberg-Universität, Duesbergweg 10–14, 55099 Mainz, Germany, Fax: (+49) 6131-3925396Search for more papers by this author Rainer Herges Prof., Rainer Herges Prof. [email protected] Institut für Organische Chemie, Christian-Albrechts-Universität zu Kiel, Otto-Hahn-Platz 4, 24118 Kiel, Germany, Fax: (+49) 431-880-2440Search for more papers by this authorAndrea Papafilippopoulos Dr., Andrea Papafilippopoulos Dr. Institut für Organische Chemie, Christian-Albrechts-Universität zu Kiel, Otto-Hahn-Platz 4, 24118 Kiel, Germany, Fax: (+49) 431-880-2440Search for more papers by this authorKirsten Hess, Kirsten Hess Institut für Organische Chemie, Christian-Albrechts-Universität zu Kiel, Otto-Hahn-Platz 4, 24118 Kiel, Germany, Fax: (+49) 431-880-2440Search for more papers by this authorCinzia Chiappe Prof., Cinzia Chiappe Prof. Dipartimento di Chimica Bioorganica e Biofarmacia, Università di Pisa, Via Bonanno 33, 56126 Pisa, ItalySearch for more papers by this authorDieter Lenoir Prof., Dieter Lenoir Prof. [email protected] Institut für Ökologische Chemie, GSF-Forschungszentrum für Umwelt und Gesundheit, Postfach 1129, 85778 Neuherberg, Germany, Fax: (+49) 89-3187-3371Search for more papers by this authorHeiner Detert Dr., Heiner Detert Dr. [email protected] Institut für Organische Chemie, Johannes Gutenberg-Universität, Duesbergweg 10–14, 55099 Mainz, Germany, Fax: (+49) 6131-3925396Search for more papers by this author First published: 15 February 2005 https://doi.org/10.1002/anie.200461632Citations: 16 † We are grateful to the Fonds der Chemischen Industrie and the Deutsche Forschungsgemeinschaft for financial support. 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 Surprising insight into a classical mechanism is provided by theoretical and experimental investigations on the bromination of alkynes. In nonpolar solvents the bromination of acetylene via a covalent tribromide adduct is strongly favored over the textbook mechanism via a bridged bromirenium ion. The structurally interesting intermediate explains the syn selectivity of the bromination of strained cycloalkynes. Supporting Information Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2005/z461632_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 1H. S. Davis, J. Am. Chem. Soc. 1928, 50, 2769–2780. 2D. M. Williams, J. Chem. Soc. Abstr. 1932, 2911–2915. 3S. Kammermeier, R. Herges, unpublished results. 4Review on alkenes: M.-F. Ruasse, Adv. Phys. Org. Chem. 1993, 28, 207. 5Review on alkynes: G. Melloni, G. Modena, U. Tonellato, Acc. Chem. Res. 1981, 14, 227–233. 6M.-F. Ruasse, G. L. Moro, B. Galland, R. Bianchini, C. Chiappe, G. Bellucci, J. Am. Chem. Soc. 1997, 119, 12 492–12 502. 7V. F. Anikin, V. V. Veduta, A. Merz, Monatsh. Chem. 1999, 130, 681–690. 8G. Bellucci, C. Chiappe, R. Bianchini, P. Lemmen, D. 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Soc. 2001, 123, 4787–4795. 22There is no minimum for a contact ion pair composed of the bromirenium cation and a tribromide anion at the levels of theory that we applied (B3LYP/6-31G*, B3LYP/6-31(2d,f), MP2/6-31G*). The stationary point of lowest order that was found for such a species is the C2v-symmetrical structure 12 b (saddle point). Structure 12 b is suitable as a model to estimate the lower level of the relative energy because the charges come very close to each other and hence minimize the dipole moment. 23S. Miertus, J. Tomasi, Chem. Phys. 1982, 65, 239–245. 24S. Miertus, E. Scrocco, J. Tomasi, Chem. Phys. 1981, 55, 117–129. 25M. Cossi, M. Persico, J. Tomasi, J. Am. Chem. Soc. 1994, 116, 5373–5378. 26We are grateful to Prof. Dr. R. Boese, Universität Essen, for his attempts to determine the X-ray structure of the intermediate in the bromination of 4. Citing Literature Volume44, Issue9February 18, 2005Pages 1412-1416 ReferencesRelatedInformation
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