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C8K-Promoted Self-Condensation and Self-Condensation-Cycloisomerization Reactions of ,-Unsaturated Fischer Carbene Complexes

2002; Wiley; Volume: 41; Issue: 18 Linguagem: Inglês

10.1002/1521-3773(20020916)41

1521-3773

Miguel Á. Sierra, Pedro Ramírez‐López, Mar Gómez‐Gallego, Tore Lejon, María J. Mancheño,

Asymmetric Hydrogenation and Catalysis

Angewandte Chemie International EditionVolume 41, Issue 18 p. 3442-3445 Communication C8K-Promoted Self-Condensation and Self-Condensation-Cycloisomerization Reactions of α,β-Unsaturated Fischer Carbene Complexes† Miguel A. Sierra Prof. Dr., Miguel A. Sierra Prof. Dr. [email protected] Departamento de Química Orgánica Facultad de Química Universidad Complutense, 28040 Madrid (Spain) Fax: (+34) 91-394-4103Search for more papers by this authorPedro Ramírez-López, Pedro Ramírez-López Departamento de Química Orgánica Facultad de Química Universidad Complutense, 28040 Madrid (Spain) Fax: (+34) 91-394-4103Search for more papers by this authorMar Gómez-Gallego Prof. Dr., Mar Gómez-Gallego Prof. Dr. Departamento de Química Orgánica Facultad de Química Universidad Complutense, 28040 Madrid (Spain) Fax: (+34) 91-394-4103Search for more papers by this authorTore Lejon Prof. Dr., Tore Lejon Prof. Dr. On sabbatical leave, permanent address: Department of Chemistry University of Tromsø 9037 Tromsø (Norway)Search for more papers by this authorMaría José Mancheño Dr., María José Mancheño Dr. Departamento de Química Orgánica Facultad de Química Universidad Complutense, 28040 Madrid (Spain) Fax: (+34) 91-394-4103Search for more papers by this author Miguel A. Sierra Prof. Dr., Miguel A. Sierra Prof. Dr. [email protected] Departamento de Química Orgánica Facultad de Química Universidad Complutense, 28040 Madrid (Spain) Fax: (+34) 91-394-4103Search for more papers by this authorPedro Ramírez-López, Pedro Ramírez-López Departamento de Química Orgánica Facultad de Química Universidad Complutense, 28040 Madrid (Spain) Fax: (+34) 91-394-4103Search for more papers by this authorMar Gómez-Gallego Prof. Dr., Mar Gómez-Gallego Prof. Dr. Departamento de Química Orgánica Facultad de Química Universidad Complutense, 28040 Madrid (Spain) Fax: (+34) 91-394-4103Search for more papers by this authorTore Lejon Prof. Dr., Tore Lejon Prof. Dr. On sabbatical leave, permanent address: Department of Chemistry University of Tromsø 9037 Tromsø (Norway)Search for more papers by this authorMaría José Mancheño Dr., María José Mancheño Dr. Departamento de Química Orgánica Facultad de Química Universidad Complutense, 28040 Madrid (Spain) Fax: (+34) 91-394-4103Search for more papers by this author First published: 16 September 2002 https://doi.org/10.1002/1521-3773(20020916)41:18 3.0.CO;2-ZCitations: 40 † Financial support by the Spanish Ministerio de Ciencia y Tecnología (Grant No. BQU2001-1283) is gratefully acknowledged. P. Ramírez-López thanks the Comunidad Autónoma de Madrid for a fellowship (Programa de Incorporación de Técnicos a Grupos de Investigación). We thank Prof. L. Kr. Hansen (University of Tromsø) for the crystal-structure analysis. Dedicated to Professor William M. Horspool on the occasion of his retirement. 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 Cunning carbene chemistry: Potassium-graphite (C8K) promotes the self condensation (to give compounds 3) and self-condensation-cycloisomerization (to give compounds 4) of α,β-unsaturated Fischer carbene complexes 1 and 2, respectively. The reaction occurs through radical-anion intermediates that dimerize in a tail-to-tail fashion. Supporting Information Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2002/z18826_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 1Selected reviews on the chemistry of metal carbene (Fischer) complexes: 1aK. H. Dötz, H. Fischer, P. Hofmann, F. R. Kreissel, U. Schubert, K. Weiss, Transition Metal Carbene Complexes, Verlag Chemie, Deerfield Beach, FL, 1983; 1bK. H. Dötz, Angew. Chem. 1984, 96, 573; Angew. Chem. Int. Ed. Engl. 1984, 23, 587; 1cW. D. Wulff in Comprehensive Organic Synthesis, Vol. 5 (Ed ), Pergamon, Oxford, 1991, p. 1065; 1dL. S. Hegedus in Comprehensive Organometallic Chemistry II, Vol. 12 (Ed ), Pergamon, Oxford, 1995, p. 549; 1eD. F. Harvey, D. M. Sigano, Chem. Rev. 1996, 96, 271; 1fJ. Barluenga, F. J. Fañanás, Tetrahedron 2000, 56, 4597; 1gM. A. Sierra, Chem. Rev. 2000, 100, 3591. 2P. J. Krusic, U. Klabunde, C. P. Casey, T. F. Block, J. Am. Chem. Soc. 1976, 98, 2015. 3S. Lee, N. J. Cooper, J. Am. Chem. Soc. 1990, 112, 9419. 4K. Fuchibe, N. Iwasawa, Org. Lett. 2000, 2, 3297. 5Reviews: 5aA. de Meijere, H. Schirmer, M. Duetsch, Angew. Chem. 2000, 112, 4124; Angew. Chem. Int. Ed. 2000, 39, 3964; 5bR. Aumann, H. Nienaber, Adv. Organomet. Chem. 1997, 41, 163. 6 6aM. Gómez-Gallego, M. J. Mancheño, P. Ramírez, C. Piñar, M. A. Sierra, Tetrahedron 2000, 56, 4893; 6bM. J. Mancheño, M. A. Sierra, M. Gómez-Gallego, P. Ramírez, Organometallics 1999, 18, 3252. 7For related rearrangements with other simple nucleophiles see: 7aJ. Barluenga, E. Rubio, J. A. López-Pelegrín, M. Tomás, Angew. Chem. 1999, 111, 1163; Angew. Chem. Int. Ed. 1999, 38, 1091. For additions of dihydropyridines see: 7bH. Rudler, A. Parlier, B. Martín-Vaca, E. Garrier, J. Vaissermann, Chem. Commun. 1999, 1439; 7cH. Rudler, A. Parlier, V. Certal, J. Vaissermann, Angew. Chem. 2000, 112, 3559; Angew. Chem. Int. Ed. 2000, 39, 3417. 8Reviews: 8aR. Csuk, B. I. Glänzer, A. Fürstner, Adv. Organomet. Chem. 1988, 28, 85; 8bD. Savoia, C. Trombini, A. Umani-Ronchi, Pure Appl. Chem. 1985, 57, 1887. 9M. A. Schwindt, T. Lejon, L. S. Hegedus, Organometallics 1990, 9, 2814. 10Structure of 9 a was elucidated by X-ray crystallography. Crystal data: Mr=510.45, orthorhombic, space group=Pc21n, a=10.174(4), b=12.653(3), c=19.559(9) Å, V=2517.9(16) Å3, Z=4, ρ=1.349 Mg m−3, MoKα=0.71069 Å, μ=0.498 mm−1, R=0.0385, Rw=0.1210, 2315 reflections, 319 refined parameters; refinement on F2. The data were collected with an Enraf-Nonius CAD-4 diffractometer (T=298(2) K). The structure and the refinement of the crystal structure were done with the SHELX97 program. The non-hydrogen atoms were refined anisotropically. CCDC-180496 (9 a) contains 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]). 11 11aM. Contento, D. Savoia, C. Trombini, A. Umani-Ronchi, Synthesis 1979, 30; For reductive dimerization of α,β-unsaturated esters see: 11bJ. Inanaga, Y. Handa, T. Tabuchi, K. Otsubo, M. Yamaguchi, T. Hanamoto, Tetrahedron Lett. 1991, 32, 6557; 11cK. Takaki, F. Beppu, S. Tanaka, Y. Tsubaki, T. Jintoku, Y. Fujiwara, J. Chem. Soc. Chem. Commun. 1990, 516; 11dI. Fussing, O. Hammerich, A. Hussain, M. Folmer Nielsen, J. H. P. Utley, Acta Chem. Scand. 1998, 52, 328. 12The percentages of deuterium incorporation in compounds 8 e and 9 c (>99 % in each case) were determined by 1H NMR. For compound 9 c the percentages of deuteration were D3: 100 % and D5: 70 %. 13The dimerization of chromium carbene α anions is known. 13aL. Lattuada, E. Licandro, S. Maiorana, H. Molinari, A. Papagni, Organometallics 1991, 10, 807; 13bA. Geisbauer, S. Mihan, W. Beck, J. Organomet. Chem. 1995, 501, 61. 14 14aH.-P. Wu, R. Aumann, R. Fröhlich, B. Wibbeling, O. Kataeva, Chem. Eur. J. 2001, 7, 5084; 14bK. Ohe, T. Yokoi, K. Miki, F. Nishino, S. Uemura, J. Am. Chem. Soc. 2002, 124, 526; 14cT. Miura, N. Iwasawa, J. Am. Chem. Soc. 2002, 124, 518; For related cyclizations see: 14dJ. Barluenga, F. Aznar, S. Barluenga, M. Fernández, A. Martín, S. García-Granda, A. Piñera-Nicolás, Chem. Eur. J. 1998, 4, 2280. 15A reviewer has suggested an alternate mechanism. Monoprotonation of 13 would give intermediate 17 which by cyclization by the addition of the enolate anion of one carbene complex to the other neutral carbene would yield the final product 9. 16 16aM. A. Sierra, M. J. Mancheño, E. Sáez, J. C. del Amo, J. Am. Chem. Soc. 1998, 120, 6812; 16bM. A. Sierra, J. C. del Amo, M. J. Mancheño, M. Gómez-Gallego, J. Am. Chem. Soc. 2001, 123, 851. 17Compounds 16 were unstable products and considerable loss of material was observed upon chromatographic purification. 18R. Aumann, Eur. J. Org. Chem. 2000, 17. 19Complexes 6 and 7 were prepared by procedures previously described in the literature. 19a6 a–d: R. Aumann, H. Heinen, Chem. Ber. 1987, 120, 537; 19b7 a: R. Aumann, P. Hinterding, Chem. Ber. 1993, 126, 421; 19c7 b: I. Fernández, M. A. Sierra, M. J. Mancheño, M. Gómez-Gallego, S. Ricart, Organometallics 2001, 20, 4304. Citing Literature Volume41, Issue18September 16, 2002Pages 3442-3445 ReferencesRelatedInformation