Subscribe to RSS
Please copy the URL and add it into your RSS Feed Reader.
https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000084.xml
Synthesis 2015; 47(04): 538-548
DOI: 10.1055/s-0034-1379486
DOI: 10.1055/s-0034-1379486
paper
A Convenient Synthesis of Functionalized Azulenes via Negishi Cross-Coupling
Further Information
Publication History
Received: 23 September 2014
Accepted after revision: 08 October 2014
Publication Date:
12 November 2014 (online)
![](https://www.thieme-connect.de/media/synthesis/201504/lookinside/thumbnails/10.1055-s-0034-1379486-1.jpg)
Abstract
A mild and effective method for the synthesis of functionalized azulenes is described. Negishi cross-coupling of bromoazulenes with functionalized aromatic, heterocyclic, benzylic, and alkylic organozinc reagents affords substituted azulenes in good yields. Functional groups, including ethoxycarbonyl, cyano, methoxy, fluoro, chloro, and bromo are well tolerated. Additionally, a one-pot procedure for introducing two different substituents into positions 1 and 3 of azulene through cross-coupling reaction is described for the first time.
Supporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0034-1379486.
- Supporting Information
-
References
- 1 Kedziorek M, Mayer P, Mayr H. Eur. J. Org. Chem. 2009; 1202
- 2 Berger S, Sicker D. Classics in Spectroscopy: Isolation and Structure Elucidation of Natural Products. Wiley-VCH; Weinheim: 2009: 153
- 3 Opdyke DL. J. Food Cosmet. Toxicol. 1974; 12: 905
- 4 Yang X.-L, Luo D.-Q, Dong Z.-J, Liu J.-K. Helv. Chim. Acta 2006; 89: 988
- 5 Harmon AD, Weisgraber KH, Weiss U. Cell. Mol. Life Sci. 1979; 36: 54
- 6 Nakamura H, Sekido M, Yamamoto Y. J. Med. Chem. 1997; 40: 2825
- 7 Tomiyama T, Yokota M, Wakabayashi S, Kosakai K, Yanagisawa T. J. Med. Chem. 1993; 36: 791
- 8 Asato AE, Peng A, Hossain MZ, Mirzadegan T, Bertram JS. J. Med. Chem. 1993; 36: 3137
- 9a Wakabayashi H, Hashiba K, Yokoyama K, Hashimoto K, Kikuchi H, Nishikawa H, Kurihara T, Satoh K, Shioda S, Sato S, Kusano S, Nakashima H, Motohashi N, Sakagami H. Anticancer Res. 2003; 23: 4747
- 9b Ishihara M, Wakabayashi H, Motohashi N, Sakagami H. Anticancer Res. 2011; 31: 515
- 10 Kamibayashi YT. M, Yamaki F, Saitoh M, Nakazawa T, Tanaka H, Noguchi K, Hashimoto K, Shigenobu K. Pharm. Pharmacol. Commun. 2000; 6: 397
- 11a Löber S, Tschammer N, Hübner H, Melis MR, Argiolas A, Gmeiner P. ChemMedChem 2009; 4: 325
- 11b Löber S, Hübner H, Buschauer A, Sanna F, Argiolas A, Melis MR, Gmeiner P. Bioorg. Med. Chem. Lett. 2012; 22: 7151
- 12 Oda M, Thanh NC, Ikai M, Fujikawa H, Nakajima K, Kuroda S. Tetrahedron 2007; 63: 10608
- 13 Ito S, Morita N. Eur. J. Org. Chem. 2009; 4567
- 14a Thanh NC, Ikai M, Kajioka T, Fujikawa H, Taga Y, Zhang Y, Ogawa S, Shimada H, Miyahara Y, Kuroda S, Oda M. Tetrahedron 2006; 62: 11227
- 14b Ito S, Shoji T, Morita N. Synlett 2011; 2279
- 14c Ito S, Terazono T, Kubo T, Okujima T, Morita N, Murafuji T, Sugihara Y, Fujimori K, Kawakami J, Tajiri A. Tetrahedron 2004; 60: 5357
- 15a Salman H, Abraham Y, Tal S, Meltzman S, Kapon M, Tessler N, Speiser S, Eichen Y. Eur. J. Org. Chem. 2005; 2207
- 15b Ito S, Okujima T, Morita N. J. Chem. Soc., Perkin Trans. 1 2002; 1896
- 16a Koch M, Blacque O, Venkatesan K. Org. Lett. 2012; 14: 1580
- 16b Fabian KH. H, Elwahy AH. M, Hafner K. Eur. J. Org. Chem. 2006; 791
- 16c Lamberto M, Pagba C, Piotrowiak P, Galoppini E. Tetrahedron Lett. 2005; 46: 4895
- 16d Ito S, Inabe H, Morita N, Ohta K, Kitamura T, Imafuku K. J. Am. Chem. Soc. 2003; 125: 1669
- 17a Shoji T, Kikuchi S, Ito S, Morita N. Heterocycles 2005; 66: 91
- 17b Shoji T, Ito S, Toyota K, Iwamoto T, Yasunami M, Morita N. Eur. J. Org. Chem. 2009; 4307
- 18 Ito S, Ueda M, Sekiguchi R, Kawakami J. Tetrahedron 2013; 69: 4259
- 19 Oda M, Kishi S, Thanh NC, Kuroda S. Heterocycles 2007; 71: 1413
- 20a Anderson AG, Nelson JA, Tazuma JJ. J. Am. Chem. Soc. 1953; 75: 4980
- 20b Rahman AF. M. M, Murafuji T, Kurotobi K, Sugihara Y, Azuma N. Organometallics 2004; 23: 6176
- 20c Nakatsuji M, Hata Y, Fujihara T, Yamamoto K, Sasaki M, Takekuma H, Yoshihara M, Minematsu T, Takekuma S.-I. Tetrahedron 2004; 60: 5983
- 21 Leermakers PA, Bowman WA. J. Org. Chem. 1964; 29: 3708
- 22 Barder TE, Walker SD, Martinelli JR, Buchwald SL. J. Am. Chem. Soc. 2005; 127: 4685
- 23 Manolikakes G, Knochel P. Angew. Chem. Int. Ed. 2009; 48: 205
- 24 Wakabayashi S, Kato Y, Mochizuki K, Suzuki R, Matsumoto M, Sugihara Y, Shimizu M. J. Org. Chem. 2007; 72: 744
- 25 Porsch M, Sigl-Seifert G, Daub J. Adv. Mater. 1997; 9: 635