Intramolecular Polar [4 ⊕ +2] Cycloadditions of Aryl‐1‐aza‐2‐azoniaallene Salts: Unprecedented Reactivity Leading to Polycyclic Protonated Azomethine Imines
2013; Wiley; Volume: 52; Issue: 50 Linguagem: Inglês
10.1002/anie.201306553
ISSN1521-3773
AutoresDaniel A. Bercovici, Jodi M. Ogilvie, Nikolay P. Tsvetkov, Matthias Brewer,
Tópico(s)Organic Chemistry Cycloaddition Reactions
ResumoAngewandte Chemie International EditionVolume 52, Issue 50 p. 13338-13341 Communication Intramolecular Polar [4⊕+2] Cycloadditions of Aryl-1-aza-2-azoniaallene Salts: Unprecedented Reactivity Leading to Polycyclic Protonated Azomethine Imines† Dr. Daniel A. Bercovici, Dr. Daniel A. Bercovici Department of Chemistry, University of Vermont, 82 University Place, Burlington, VT 05405 (USA) These authors contributed equally to this work.Search for more papers by this authorDr. Jodi M. Ogilvie, Dr. Jodi M. Ogilvie Department of Chemistry, University of Vermont, 82 University Place, Burlington, VT 05405 (USA) These authors contributed equally to this work. Née Wyman.Search for more papers by this authorDr. Nikolay Tsvetkov, Dr. Nikolay Tsvetkov Department of Chemistry, University of Vermont, 82 University Place, Burlington, VT 05405 (USA)Search for more papers by this authorProf. Matthias Brewer, Corresponding Author Prof. Matthias Brewer [email protected] Department of Chemistry, University of Vermont, 82 University Place, Burlington, VT 05405 (USA)Department of Chemistry, University of Vermont, 82 University Place, Burlington, VT 05405 (USA)===Search for more papers by this author Dr. Daniel A. Bercovici, Dr. Daniel A. Bercovici Department of Chemistry, University of Vermont, 82 University Place, Burlington, VT 05405 (USA) These authors contributed equally to this work.Search for more papers by this authorDr. Jodi M. Ogilvie, Dr. Jodi M. Ogilvie Department of Chemistry, University of Vermont, 82 University Place, Burlington, VT 05405 (USA) These authors contributed equally to this work. Née Wyman.Search for more papers by this authorDr. Nikolay Tsvetkov, Dr. Nikolay Tsvetkov Department of Chemistry, University of Vermont, 82 University Place, Burlington, VT 05405 (USA)Search for more papers by this authorProf. Matthias Brewer, Corresponding Author Prof. Matthias Brewer [email protected] Department of Chemistry, University of Vermont, 82 University Place, Burlington, VT 05405 (USA)Department of Chemistry, University of Vermont, 82 University Place, Burlington, VT 05405 (USA)===Search for more papers by this author First published: 11 November 2013 https://doi.org/10.1002/anie.201306553Citations: 13 † We thank Dr. M. I. Javed for obtaining a preliminary result for this project, Bruce O'Rourke for obtaining mass spectral data, Dr. Bruce Deker for assistance with NMR characterization, and Prof. Rory Waterman for X-ray data collection and structure determination. Financial support was provided by the National Science Foundation under CHE-0748058 and through instrumentation grants CHE-1039436, CHE-1126265, and CHE-0821501. This work was made possible by use of a facility supported by the Vermont Genetics Network through Grant Number 8P20GM103449 from the INBRE Program of the National Institute of General Medical Sciences (NIGMS), a component of the National Institutes of Health (NIH). § Née Wyman. 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 Charged up: In the first example of the title salts undergoing a [4⊕+2] cycloaddition reaction, the azo bond and one aromatic π bond make up the 4π component. This reaction appears to be concerted and provides high yields of protonated azomethine imine products. Substituted alkenes provided products containing all-carbon or nitrogen-bearing quaternary centers in high yield. References 1 1aR. R. Schmidt, Angew. Chem. 1973, 85, 235– 247; Angew. Chem. Int. Ed. Engl. 1973, 12, 212– 224; 1bR. Gompper, Angew. Chem. 1969, 81, 348– 363; Angew. Chem. Int. Ed. Engl. 1969, 8, 312– 327; 1cM. N. Eberlin, Int. J. Mass Spectrom. 2004, 235, 263– 278. 2 2aW. Davies, B. C. Ennis, J. Chem. Soc. 1959, 915– 918; 2bB. I. Rosen, W. Weber, J. Org. Chem. 1977, 42, 3463– 3465; 2cW. B. Manning, T. P. Kelly, G. M. Muschik, J. Org. Chem. 1980, 45, 2535– 2536; 2dH. K. Hall, P. Nogues, J. W. Rhoades, R. C. Sentman, M. Detar, J. Org. Chem. 1982, 47, 1451– 1455; 2eE. Ciganek, J. 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Chem. 2010, 75, 8078– 8087; 12cN. Q. Al-Bataineh, M. Brewer, Tetrahedron Lett. 2012, 53, 5411– 5413. 13J. E. Baldwin, M. J. Lusch, Tetrahedron 1982, 38, 2939– 2947. 14W. Lewgowd, A. Stanczak, Arch. Pharm. 2007, 340, 65– 80. 15 15aR. N. Castle, M. Onda, J. Org. Chem. 1961, 26, 4465– 4469; 15bD. E. Ames, H. Z. Kucharska, J. Chem. Soc. 1964, 283– 289; 15cO. Diels, K. Alder, Justus Liebigs Ann. Chem. 1926, 450, 237– 254; 15dG. Cauquis, M. Genies, Tetrahedron Lett. 1970, 11, 3403– 3405; 15eW. Jugelt, S. Schwertner, Z. Chem. 1983, 23, 28– 29; 15fA. L. J. Beckwith, S. Wang, J. Warkentin, J. Am. Chem. Soc. 1987, 109, 5289– 5291. 16I. D. Jurberg, F. Gagosz, J. Organomet. Chem. 2011, 696, 37– 41. 17Protonated azomethine imines are not common species, but are known to be more stable than their deprotonated dipolar counterparts. For examples of these species, see: 17aY. Tamura, J.-I. Minamikawa, Y. Miki, Y. Okamoto, M. Ikeda, Yakugaku Zasshi 1973, 93, 648– 653; 17bT. Hashimoto, Y. Maeda, M. Omote, H. Nakatsu, K. Maruoka, J. Am. Chem. Soc. 2010, 132, 4076– 4077. 18CCDC 952450 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. 19The crude reaction mixtures were triturated with petroleum ether to provide products with minimal impurities. Attempts to further purify the products by chromatography or crystallization failed. The yields reported in Tables 1 and 2 are based on the limiting reagent (Lewis acid) and were determined by proton NMR spectoscopy using 1,3,5-trimethoxybenzene as an internal standard. 20The diastereomers were not separable and the relative configuration of the major and minor component was not determined. 21The relative configuration of 9 g–l were determined by evaluation of the coupling constants between the benzylic proton and the proton adjacent to the positively charged amine. 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