Silyl-Mediated Halogen/Halogen Displacement in Pyridines and Other Heterocycles
2002; Wiley; Volume: 2002; Issue: 24 Linguagem: Inglês
10.1002/1099-0690(200212)2002
ISSN1434-193X
AutoresManfred Schlosser, Fabrice Cottet,
Tópico(s)Synthesis and Biological Evaluation
ResumoEuropean Journal of Organic ChemistryVolume 2002, Issue 24 p. 4181-4184 Full Paper Silyl-Mediated Halogen/Halogen Displacement in Pyridines and Other Heterocycles Manfred Schlosser, Manfred Schlosser [email protected] Institut de Chimie moléculaire et biologique, Ecole Polytechnique Fédérale, BCh, 1015 Lausanne, Switzerland Faculté des Sciences, Université, BCh 1015 Lausanne, SwitzerlandSearch for more papers by this authorFabrice Cottet, Fabrice Cottet Institut de Chimie moléculaire et biologique, Ecole Polytechnique Fédérale, BCh, 1015 Lausanne, SwitzerlandSearch for more papers by this author Manfred Schlosser, Manfred Schlosser [email protected] Institut de Chimie moléculaire et biologique, Ecole Polytechnique Fédérale, BCh, 1015 Lausanne, Switzerland Faculté des Sciences, Université, BCh 1015 Lausanne, SwitzerlandSearch for more papers by this authorFabrice Cottet, Fabrice Cottet Institut de Chimie moléculaire et biologique, Ecole Polytechnique Fédérale, BCh, 1015 Lausanne, SwitzerlandSearch for more papers by this author First published: 26 November 2002 https://doi.org/10.1002/1099-0690(200212)2002:24 3.0.CO;2-MCitations: 39Read 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 Abstract Heating with bromotrimethylsilane converts 2-chloropyridine into 2-bromopyridine and 2-chloro-6-methylpyridine into 2-bromo-6-methylpyridine. Both 2-chloropyridines and 2-bromopyridines give the corresponding iodo compound when treated with in situ generated iodotrimethylsilane. Although 3- and 4-chloropyridine are completely inert, 2,4-dichloropyridine undergoes the halogen/halogen exchange simultaneously at the 2- and 4-position. Halogen displacement takes place exclusively at the 2-position with 2,3-dichloropyridine and 2,5-dichloropyridine. In agreement with the intermediacy of N-trimethylsilylpyridinium salts as a prerequisite for the occurrence of halogen exchange, neither 2-fluoropyridine and 2-fluoro-6-methylpyridine nor any 2,6-dihalopyridine reacts. Finally, bromine/chlorine and iodine/chlorine substitution can also be accomplished with 2- or 4-chloroquinoline, 1-chloroisoquinoline, 2-chloropyrimidine, chloropyrazine and 2,3-dichloroquinoxaline as substrates. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2002) References 1 M. Schlosser, in Organometallics in Synthesis: A Manual (Ed.: M. Schlosser), 2nd ed., Wiley, Chichester, 2002, p. 1−352, specially p. 95 and 134, see also p. 135−136. Google Scholar 2 F. Trécourt , G. Breton , V. Bonnet , F. Mongin , F. Marsais , G. Quéguiner , Tetrahedron 2000 , 56 , 1349 −1360 . 10.1016/S0040-4020(00)00027-2 CASWeb of Science®Google Scholar 3 T. Iida , T. Wada , K. Tomimoto , T. Mase , Tetrahedron Lett. 2001 , 42 , 4841 −4844 . 10.1016/S0040-4039(01)00861-9 CASWeb of Science®Google Scholar 4 F. Cottet , M. Schlosser , Eur. J. Org. Chem. 2002 , 327 −330 . 10.1002/1099-0690(20021)2002:2 3.0.CO;2-V CASWeb of Science®Google Scholar 5 N. Miyaura , A. Suzuki , Chem. 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