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Simple Access to Unsymmetrically Substituted, Saturated N‐Heterocyclic Carbenes

2003; Wiley; Volume: 42; Issue: 42 Linguagem: Inglês

10.1002/anie.200352349

1521-3773

F. Ekkehardt Hahn, Martin Paas, Duc Le Van, Thomas Lügger,

Synthetic Organic Chemistry Methods

Angewandte Chemie International EditionVolume 42, Issue 42 p. 5243-5246 Communication Simple Access to Unsymmetrically Substituted, Saturated N-Heterocyclic Carbenes† F. Ekkehardt Hahn Prof. Dr., F. Ekkehardt Hahn Prof. Dr. [email protected] Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Wilhelm-Klemm-Strasse 8, 48 149 Münster, Germany, Fax: (+49) 251-833-3293Search for more papers by this authorMartin Paas Dipl.-Chem., Martin Paas Dipl.-Chem. Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Wilhelm-Klemm-Strasse 8, 48 149 Münster, Germany, Fax: (+49) 251-833-3293Search for more papers by this authorDuc Le Van Dr., Duc Le Van Dr. Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Wilhelm-Klemm-Strasse 8, 48 149 Münster, Germany, Fax: (+49) 251-833-3293Search for more papers by this authorThomas Lügger Dr., Thomas Lügger Dr. Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Wilhelm-Klemm-Strasse 8, 48 149 Münster, Germany, Fax: (+49) 251-833-3293Search for more papers by this author F. Ekkehardt Hahn Prof. Dr., F. Ekkehardt Hahn Prof. Dr. [email protected] Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Wilhelm-Klemm-Strasse 8, 48 149 Münster, Germany, Fax: (+49) 251-833-3293Search for more papers by this authorMartin Paas Dipl.-Chem., Martin Paas Dipl.-Chem. Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Wilhelm-Klemm-Strasse 8, 48 149 Münster, Germany, Fax: (+49) 251-833-3293Search for more papers by this authorDuc Le Van Dr., Duc Le Van Dr. Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Wilhelm-Klemm-Strasse 8, 48 149 Münster, Germany, Fax: (+49) 251-833-3293Search for more papers by this authorThomas Lügger Dr., Thomas Lügger Dr. Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Wilhelm-Klemm-Strasse 8, 48 149 Münster, Germany, Fax: (+49) 251-833-3293Search for more papers by this author First published: 30 October 2003 https://doi.org/10.1002/anie.200352349Citations: 84 † Financial support for this work was provided by the Deutsche Forschungsgemeinschaft, the NRW Graduate School of Chemistry Münster, and the Fonds der Chemischen Industrie. 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 Secondary amines and imines were used to prepare unsymmetrically substituted, non-aromatic N-heterocyclic carbenes via imidazolidine-2-thiones (rac-1) as intermediates. The presence of only one sterically demanding substituent on one of the N atoms in rac-2 is sufficient to prevent dimerization to the enetetramine. Supporting Information Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2003/z52349_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 1A. J. Arduengo III, R. L. Harlow, M. Kline, J. Am. Chem. Soc. 1991, 113, 361–363. 2A. J. Arduengo III, J. R. Goerlich, W. J. Marshall, J. Am. Chem. Soc. 1995, 117, 11 027–11 028. 3 3aD. Bourissou, O. Guerret, F. P. Gabbai, G. Bertrand, Chem. Rev. 2000, 100, 39–91; 3bW. A. Herrmann, C. Köcher, Angew. Chem. 1997, 109, 2256–2282; Angew. Chem. Int. Ed. Engl. 1997, 36, 2162–2187; 3cW. A. Herrmann, Angew. Chem. 2002, 114, 1343–1363; Angew. Chem. Int. Ed. 2002, 41, 1290–1309. 4 4aM. K. Denk, A. Thadani, K. Hatano, A. J. Lough, Angew. Chem. 1997, 109, 2719–2721; Angew. Chem. 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Chem. 2002, 649, 219–224. 20X-ray crystal-structure analyses: rac-9 a (C19H34ClN2Rh): M=428.84, yellow crystal, 0.09×0.09×0.09 mm3, a=13.3236(8), b=10.1380(6), c=14.3124(9) Å, β=99.9730(10)°, V=1904.0(2) Å3, ρcalcd=1.496 g cm−3, μ=1.039 mm−1, semiempirical absorption correction, ω and ϕ scans, 20 920 measured intensities, 5520 independent (Rint=0.0312) and 4907 observed (I⩾2σ(I)) intensities, λ=0.71073 Å, T=173(2) K, Z=4, P21/c, R=0.0313, wR2=0.0673 (refinement against |F2| with H atoms at calculated positions); rac-9 b (C22H40ClN2Rh): M=470.92, yellow crystal, 0.12×0.09×0.07 mm3, a=26.950(3), b=11.2303(14), c=31.436(4) Å, β=107.863(3)°, V=9056(2) Å3, ρcalcd=1.382 g cm−3, μ=0.881 mm−1, semiempirical absorption correction (0.9017⩽T⩽0.9409), ω and ϕ scans, 87 982 measured intensities, 20 883 independent (Rint=0.0854) and 15 220 observed (I⩾2σ(I)) intensities, λ=0.71073 Å, T=153(2) K, Z=16, P21/n, R=0.0544, wR2=0.1122 (refinement against |F2| with H atoms at calculated positions). CCDC-213 748 (rac-9 a) and -213 949 (rac-9 b) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or [email protected]). Citing Literature Volume42, Issue42November 3, 2003Pages 5243-5246 ReferencesRelatedInformation