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Sigmatropic Shifts in Allene Oxide Rearrangements: First General Route to [3,4] Shifts in Aliphatic Systems

1997; Wiley; Volume: 36; Issue: 13-14 Linguagem: Inglês

10.1002/anie.199715161

1521-3773

Ihsan Erden, Fupei Xu, Weiguo Cao,

Catalytic C–H Functionalization Methods

Angewandte Chemie International Edition in EnglishVolume 36, Issue 13-14 p. 1516-1518 Communication Sigmatropic Shifts in Allene Oxide Rearrangements: First General Route to [3,4] Shifts in Aliphatic Systems† Prof. Dr. Ihsan Erden, Corresponding Author Prof. Dr. Ihsan Erden Department of Chemistry and Biochemistry, San Francisco State University, 1600 Holloway Avenue, San Francisco, CA 94132 (USA), Fax: Int. code +(415)338-2384, e-mail: [email protected]Department of Chemistry and Biochemistry, San Francisco State University, 1600 Holloway Avenue, San Francisco, CA 94132 (USA), Fax: Int. code +(415)338-2384, e-mail: [email protected]Search for more papers by this authorDr. Fu-Pei Xu, Dr. Fu-Pei Xu Department of Chemistry and Biochemistry, San Francisco State University, 1600 Holloway Avenue, San Francisco, CA 94132 (USA), Fax: Int. code +(415)338-2384, e-mail: [email protected]Search for more papers by this authorWei-Guo Cao, Wei-Guo Cao Department of Chemistry and Biochemistry, San Francisco State University, 1600 Holloway Avenue, San Francisco, CA 94132 (USA), Fax: Int. code +(415)338-2384, e-mail: [email protected]Search for more papers by this author Prof. Dr. Ihsan Erden, Corresponding Author Prof. Dr. Ihsan Erden Department of Chemistry and Biochemistry, San Francisco State University, 1600 Holloway Avenue, San Francisco, CA 94132 (USA), Fax: Int. code +(415)338-2384, e-mail: [email protected]Department of Chemistry and Biochemistry, San Francisco State University, 1600 Holloway Avenue, San Francisco, CA 94132 (USA), Fax: Int. code +(415)338-2384, e-mail: [email protected]Search for more papers by this authorDr. Fu-Pei Xu, Dr. Fu-Pei Xu Department of Chemistry and Biochemistry, San Francisco State University, 1600 Holloway Avenue, San Francisco, CA 94132 (USA), Fax: Int. code +(415)338-2384, e-mail: [email protected]Search for more papers by this authorWei-Guo Cao, Wei-Guo Cao Department of Chemistry and Biochemistry, San Francisco State University, 1600 Holloway Avenue, San Francisco, CA 94132 (USA), Fax: Int. code +(415)338-2384, e-mail: [email protected]Search for more papers by this author First published: August 4, 1997 https://doi.org/10.1002/anie.199715161Citations: 17 † This work was supported by the U. S. National Foundation (grant no. CHE-89044016). AboutPDF 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 The 3-butenyl group makes it possible. The saturated endoperoxide 1 reacts at 60–80°C via the allene oxide 2 and its ring-opened product 3 by a [3,4]-sigmatropic shift to form the 5-oxo-6-heptenal derivatives 4. The reaction might also be applicable to heteroatom analogues of 1. References 1 I. Erden, M. Amputch, Tetrahedron Lett. 1987, 28, 3779. 2 I. Erden, J. Drummond, R. Alstad, F.-P. Xu, Tetrahedron Lett. 1993, 34, 1255. 3 I. Erden, J. Drummond, R. Alstad, F.-P. Xu, Tetrahedron Lett. 1993, 34, 2291. 4 I. Erden, F.-P. Xu, J. Drummond, R. Astad, J. Org. Chem. 1993, 58, 3611. 5(a) H.-J. Hansen, B. Sutter, H. Schmid, Helv. Chim. Acta 1968, 51, 828; (b) H. Heimgartner, J. Zsindeley, H.-J. Hansen, H. Schmid, Helv. Chim. Acta 1972, 55, 1113; (c) U. Widmer, H.-J. Hansen, H. Schmid, Helv. Chim. Acta 1973, 56, 1895; see also (d) K. C. Masumdar, A. T. Khan, S. K. Chattopadhyay, J. Chem. Soc. Perkin Trans 1 1990, 2219. 6 P. Viltrorelli, J. Peter-Katalinic, G. Mukherje-Müller, H.-J. Hansen, H. Schmid, Helv. Chim. Acta 1975, 58, 1379. 7 The other example of a [3,4] shift in an aliphatic compound involves a 2-oxyallyl/FeII species that was generated from the corresponding α, α-dibromo ketone with [Fe2(CO)9] and observed in one isolated case: M. Nishizawa, R. Noyori, Bull. Chem. Soc. Jpn. 1981, 54, 2233. 8 M. J. S. Dewar, Angew. Chem. 1971, 83, 859; Angeww. Chem. Int. Ed. Engl. 1971, 10, 761. 9 Most of the requisite fulvenes were prepared from the corresponding carbonyl compounds and cyclopentadiene by Little's method: (a) K. Stone, R. D. Little, J. Org. Chem. 1984, 49, 1849. Fulvenes 13 and 14 were obtained with NaOMe as base: (b) I. Erden, F.-P. Xu, A. Sadoun, G. Sheff, M. Ossun, J. Org. Chem. 1995, 60, 813. Endoperoxides 9–14 were prepared by low-temperature photooxoygenation of the respective fulvenes at −78°C followed by diazene reduction of the unsaturated endoperoxides at about −40°C [1.10]. 10 W. Adam, I. Erden, Angew. Chem. 1978, 90 223; Angew. Chem. Int. Ed. Engl. 1978, 17, 210. 11 R. B. Woodward, R. Hoffmann, The Cosnservation of Orbital Symmetry, Academic Press, New York, 1970, p. 130. 12 I. Fleming, Frontier Orbitals and Organic Chemical Reactions, Wiley, New York, 1975, p. 86. 13 T. S. Sorensen, A. Rauk, Pericyclic Reactions, Vol. II (Eds.: A. P. Marchand, R. E. Lehr), Academic Press, New York, 1977, p. 64. 14 A homo-Cope rearrangement via a cyclopropanone intermediate might also be considered as an alternative to the [3,4] shift: (a) D. Hochstrate, F.-G. Klärner, Liebigs. Ann. 1995, 745; see also (b) W. R. Roth, H.-W. Lennartz, W. V. E. Doering, L. Birladeanu, C. A. Guyton, T. Kitagawa, J. Am. Chem. Soc. 1990, 112, 1723. Citing Literature Volume36, Issue13-14August 4, 1997Pages 1516-1518 ReferencesRelatedInformation