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Complete Stereospecific Cyclopropanation of α,β-Unsaturated Amides Promoted by Sm/CH2I2 We acknowledge financial support from II Plan Regional de Investigación del Principado de Asturias (PB-EXP01-11) and Ministerio de Ciencia y Tecnología (BQU2001-3807). We thank Dr. Francisco J. González for valuable discussions and Robin Walker for revising the English manuscript. J.M.C. thanks Carmen Fernández-Flórez for her time. H.R.S. thanks Principado de Asturias for a predoctoral fellowship.

2002; Wiley; Volume: 41; Issue: 11 Linguagem: Inglês

10.1002/1521-3773(20020603)41

1521-3773

José M. Concellón, Humberto Rodríguez‐Solla, Cecilia Gómez,

Asymmetric Synthesis and Catalysis

Angewandte Chemie International EditionVolume 41, Issue 11 p. 1917-1919 Communication Complete Stereospecific Cyclopropanation of α,β-Unsaturated Amides Promoted by Sm/CH2I2 José M. Concellón Dr., José M. Concellón Dr. [email protected] Departamento de Química Orgánica e Inorgánica Facultad de Química, Universidad de Oviedo 33071 Oviedo (Spain) Fax: (+34) 98-510-3446Search for more papers by this authorHumberto Rodríguez-Solla, Humberto Rodríguez-Solla Departamento de Química Orgánica e Inorgánica Facultad de Química, Universidad de Oviedo 33071 Oviedo (Spain) Fax: (+34) 98-510-3446Search for more papers by this authorCecilia Gómez Dr., Cecilia Gómez Dr. Departamento de Química Orgánica Facultad de Ciencias, Universidad de Alicante Apartado 99, 03080 Alicante (Spain)Search for more papers by this author José M. Concellón Dr., José M. Concellón Dr. [email protected] Departamento de Química Orgánica e Inorgánica Facultad de Química, Universidad de Oviedo 33071 Oviedo (Spain) Fax: (+34) 98-510-3446Search for more papers by this authorHumberto Rodríguez-Solla, Humberto Rodríguez-Solla Departamento de Química Orgánica e Inorgánica Facultad de Química, Universidad de Oviedo 33071 Oviedo (Spain) Fax: (+34) 98-510-3446Search for more papers by this authorCecilia Gómez Dr., Cecilia Gómez Dr. Departamento de Química Orgánica Facultad de Ciencias, Universidad de Alicante Apartado 99, 03080 Alicante (Spain)Search for more papers by this author First published: 28 May 2002 https://doi.org/10.1002/1521-3773(20020603)41:11 3.0.CO;2-1Citations: 18 We acknowledge financial support from II Plan Regional de Investigación del Principado de Asturias (PB-EXP01-11) and Ministerio de Ciencia y Tecnología (BQU2001-3807). We thank Dr. Francisco J. González for valuable discussions and Robin Walker for revising the English manuscript. J.M.C. thanks Carmen Fernández-Flórez for her time. H.R.S. thanks Principado de Asturias for a predoctoral fellowship. 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 Samarium learns another trick: Complete stereospecific cyclopropanation of α,β-unsaturated amides, in which the double bond is di-, tri-, or tetrasubstituted is promoted by Sm/CH2I2 [Eq. (1)]. The reaction is high yielding and unaffected by the bulk of the substituents R1–R4. Supporting Information Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2002/z18547_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 1 1a "Biochemistry of the Cyclopropyl Group": H. W. Liu, C. T. Walsh in The Chemistry of the Cyclopropyl Group ( ), Wiley, New York, 1987, chap. 16, pp. 959–1025; 1b R. Faust, Angew. Chem. 2001, 113, 2312–2314; Angew. Chem. Int. Ed. 2001, 40, 2251–2253; 1c W. A. Donaldson, Tetrahedron 2001, 57, 8589–8627; 1d J. Salaün, Top. Curr. Chem. 2000, 207, 1–67. 2 2a G. Maier, S. Senger, Angew. Chem. 1994, 106, 605–606; Angew. Chem. Int. Ed. Engl. 1994, 33, 558–559; 2b L. Dechoux, E. Doris, Tetrahedron Lett. 1994, 35, 2017–2020; 2c R. B. Silverman, Y. Zelechonok, J. Org. 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Rev. 1997, 97, 2341–2372. 9 E. V. Dehmlow, K. Eulenberg, Liebigs Ann. Chem. 1978, 1112–1115. 10 For recent reports on the cyclopropanation of α,β-unsaturated amides see: 10a S. Goumri-Magnet, T. Kato, H. Gornitzka, A. Baceiredo, G. Bertrand, J. Am. Chem. Soc. 2000, 122, 4464–4470; 10b S. Ye, L. Yuan, Z. Z. Huang, Y. Tang, L. X. Dai, J. Org. Chem. 2000, 65, 6257–6260; 10c A. Mamai, J. S. Madalengoitia, Tetrahedron Lett. 2000, 41, 9009–9014. 11 11a G. A. Molander, J. B. Etter, J. Org. Chem. 1987, 52, 3942–3944; 11b G. A. Molander, L. S. Harring, J. Org. Chem. 1989, 54, 3525–3532. 12 T. Imamoto, N. Takiyama, Tetrahedron Lett. 1987, 28, 1307–1308. 13 Previously, it was indicated that the cyclopropanation promoted by samarium carbenoids takes place exclusively with allylic alcohols, and other functionalized olefinic substrates are inert (see ref. [11b]). 14 J. M. Concellón, P. L. Bernad, J. A. Pérez-Andrés, Angew. Chem. 1999, 111, 2528–2530; Angew. Chem. Int. Ed. 1999, 38, 2384–2386. 15 J. M. Concellón, J. A. Pérez-Andrés, H. Rodríguez-Solla, Angew. Chem. 2000, 112, 2866–2868; Angew. Chem. Int. Ed. 2000, 39, 2773–2775. 16 J. M. Concellón, J. A. Pérez-Andrés, H. Rodríguez-Solla, Chem. Eur. J. 2001, 7, 3062–3068. 17 J. M. Concellón, P. L. Bernad, H. Rodríguez-Solla, Angew. Chem. 2001, 113, 4015–4017; Angew. Chem. Int. Ed. 2001, 40, 3897–3899. 18 J. M. Concellón, P. L. Bernad, E. Bardales, Org. Lett. 2001, 3, 937–939. 19 The product of double cyclopropanation was obtained in 2 % yield (GC-MS). 20 "Nuclear Magnetic Resonance and Infrared Spectra of Cyclopropanes and Cyclopropenes": D. G. Morris in The Chemistry of the Cyclopropyl Group ( ), Wiley, New York, 1987, chap. 3, pp. 101–172. 21 When the reaction time is increased, the yield of some Simmon–Smith cyclopropanations decrease: C. D. Poulter, E. C. Fiedrich, S. Winstein, J. Am. Chem. Soc. 1969, 91, 6892–6894. 22 22a J. L. Namy, P. E. Caro, P. Girard, H. B. Kagan, Nouv. J. Chim. 1981, 5, 479–484; 22b T. Imamoto, H. Koto, T. Takeyama, Tetrahedron Lett. 1986, 27, 3243–3246; 22c T. Tabuchi, J. Inanaga, M. Yamaguchi, Tetrahedron Lett. 1986, 27, 3891–3894. 23 23a M. N. Paddon-Row, N. G. Rondan, K. N. Houk, J. Am. Chem. Soc. 1982, 104, 7162–7166; 23b J. Mareda, N. G. Rondan, K. N. Houk, J. Am. Chem. Soc. 1983, 105, 6997–6999. Citing Literature Volume41, Issue11June 3, 2002Pages 1917-1919 ReferencesRelatedInformation