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A Search for Unambiguous Vinylic SRN1 Reactions

2002; Wiley; Volume: 2002; Issue: 13 Linguagem: Inglês

10.1002/1099-0690(200207)2002

1434-193X

Alfonso Annunziata, Carlo Galli, Patrizia Gentili, Alessandra Guarnieri, Michal Beit-Yannai, Zvi Rappoport,

Chemical Synthesis and Analysis

European Journal of Organic ChemistryVolume 2002, Issue 13 p. 2136-2143 Full Paper A Search for Unambiguous Vinylic SRN1 Reactions Alfonso Annunziata, Alfonso Annunziata Dipartimento di Chimica and Centro CNR Meccanismi di Reazione, Università “La Sapienza”, P.le Aldo Moro 5, 00185 Roma, Italy, Fax: (internat.) + 39-06/490421Search for more papers by this authorCarlo Galli, Carlo Galli carlo.galli@uniroma1.it Dipartimento di Chimica and Centro CNR Meccanismi di Reazione, Università “La Sapienza”, P.le Aldo Moro 5, 00185 Roma, Italy, Fax: (internat.) + 39-06/490421Search for more papers by this authorPatrizia Gentili, Patrizia Gentili Dipartimento di Chimica and Centro CNR Meccanismi di Reazione, Università “La Sapienza”, P.le Aldo Moro 5, 00185 Roma, Italy, Fax: (internat.) + 39-06/490421Search for more papers by this authorAlessandra Guarnieri, Alessandra Guarnieri Dipartimento di Chimica and Centro CNR Meccanismi di Reazione, Università “La Sapienza”, P.le Aldo Moro 5, 00185 Roma, Italy, Fax: (internat.) + 39-06/490421Search for more papers by this authorMichal Beit-Yannai, Michal Beit-Yannai Department of Organic Chemistry, The Hebrew University, Jerusalem 91904, IsraelSearch for more papers by this authorZvi Rappoport, Zvi Rappoport Department of Organic Chemistry, The Hebrew University, Jerusalem 91904, IsraelSearch for more papers by this author Alfonso Annunziata, Alfonso Annunziata Dipartimento di Chimica and Centro CNR Meccanismi di Reazione, Università “La Sapienza”, P.le Aldo Moro 5, 00185 Roma, Italy, Fax: (internat.) + 39-06/490421Search for more papers by this authorCarlo Galli, Carlo Galli carlo.galli@uniroma1.it Dipartimento di Chimica and Centro CNR Meccanismi di Reazione, Università “La Sapienza”, P.le Aldo Moro 5, 00185 Roma, Italy, Fax: (internat.) + 39-06/490421Search for more papers by this authorPatrizia Gentili, Patrizia Gentili Dipartimento di Chimica and Centro CNR Meccanismi di Reazione, Università “La Sapienza”, P.le Aldo Moro 5, 00185 Roma, Italy, Fax: (internat.) + 39-06/490421Search for more papers by this authorAlessandra Guarnieri, Alessandra Guarnieri Dipartimento di Chimica and Centro CNR Meccanismi di Reazione, Università “La Sapienza”, P.le Aldo Moro 5, 00185 Roma, Italy, Fax: (internat.) + 39-06/490421Search for more papers by this authorMichal Beit-Yannai, Michal Beit-Yannai Department of Organic Chemistry, The Hebrew University, Jerusalem 91904, IsraelSearch for more papers by this authorZvi Rappoport, Zvi Rappoport Department of Organic Chemistry, The Hebrew University, Jerusalem 91904, IsraelSearch for more papers by this author First published: 14 June 2002 https://doi.org/10.1002/1099-0690(200207)2002:13 3.0.CO;2-8Citations: 11Read 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 onFacebookTwitterLinkedInRedditWechat Abstract In a search for unambiguous examples of the vinylic SRN1 route, vinyl bromides Ph(CH3)C=CHBr (10), Ph2C=CHBr (15), An2C=C(Br)An (18) and An2C=CBr2 (20) were treated with Me3CCOCH2− under photostimulation conditions in Me2SO, whereas substrates PhCH=CHBr (2), Ph2C=C(Br)Ph (3), 10 and 15 were similarly allowed to react with PhS− and PhCH2S−. With the strongly basic enolate ion, the prevailing reactions were elimination/addition routes, α-deprotonation followed by 1,2-Ph shift and bromide ion elimination, or halophilic steps. With 18, however, an SRN1 route was obtained. The weakly basic but reducing anion PhS− gave the SRN1 route with 2, 3 and 15. The nucleophilic character of the PhCH2S− anion instead prevailed with 15, whereas with 3 a variety of behaviours was obtained. The mechanistic interpretations were supported by the electrochemically determined redox potentials of the substrates. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002) Citing Literature Supporting Information Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2046/2002/o02043_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. Volume2002, Issue13July 2002Pages 2136-2143 RelatedInformation