Voltar
Artigo Acesso aberto Revisado por pares
BIBTEX RIS

FeCl 3 ‐Mediated Friedel–Crafts Hydroarylation with Electrophilic N ‐Acetyl Indoles for the Synthesis of Benzofuroindolines

2012; Wiley; Volume: 51; Issue: 50 Linguagem: Inglês

10.1002/anie.201206611

ISSN

1521-3773

Autores

Rodolphe Beaud, Régis Guillot, Cyrille Kouklovsky, Guillaume Vincent,

Tópico(s)

Chemical Synthesis and Reactions

Resumo

Angewandte Chemie International EditionVolume 51, Issue 50 p. 12546-12550 Communication FeCl3-Mediated Friedel–Crafts Hydroarylation with Electrophilic N-Acetyl Indoles for the Synthesis of Benzofuroindolines† Rodolphe Beaud, Rodolphe Beaud Université Paris-Sud and CNRS, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), UMR 8182, Laboratoire de Chimie des Procédés et Substances Naturelles, Bat. 410, 91405 Orsay (France) http://www.icmmo.u-psud.fr/Labos/LPSN/cv/guillaume_eng.php?ID=381Search for more papers by this authorDr. Régis Guillot, Dr. Régis Guillot Université Paris-Sud and CNRS, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), UMR 8182, Laboratoire de Chimie des Procédés et Substances Naturelles, Bat. 410, 91405 Orsay (France) http://www.icmmo.u-psud.fr/Labos/LPSN/cv/guillaume_eng.php?ID=381Search for more papers by this authorProf.Dr. Cyrille Kouklovsky, Prof.Dr. Cyrille Kouklovsky Université Paris-Sud and CNRS, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), UMR 8182, Laboratoire de Chimie des Procédés et Substances Naturelles, Bat. 410, 91405 Orsay (France) http://www.icmmo.u-psud.fr/Labos/LPSN/cv/guillaume_eng.php?ID=381Search for more papers by this authorDr. Guillaume Vincent, Corresponding Author Dr. Guillaume Vincent [email protected] Université Paris-Sud and CNRS, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), UMR 8182, Laboratoire de Chimie des Procédés et Substances Naturelles, Bat. 410, 91405 Orsay (France) http://www.icmmo.u-psud.fr/Labos/LPSN/cv/guillaume_eng.php?ID=381Université Paris-Sud and CNRS, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), UMR 8182, Laboratoire de Chimie des Procédés et Substances Naturelles, Bat. 410, 91405 Orsay (France) http://www.icmmo.u-psud.fr/Labos/LPSN/cv/guillaume_eng.php?ID=381Search for more papers by this author Rodolphe Beaud, Rodolphe Beaud Université Paris-Sud and CNRS, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), UMR 8182, Laboratoire de Chimie des Procédés et Substances Naturelles, Bat. 410, 91405 Orsay (France) http://www.icmmo.u-psud.fr/Labos/LPSN/cv/guillaume_eng.php?ID=381Search for more papers by this authorDr. Régis Guillot, Dr. Régis Guillot Université Paris-Sud and CNRS, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), UMR 8182, Laboratoire de Chimie des Procédés et Substances Naturelles, Bat. 410, 91405 Orsay (France) http://www.icmmo.u-psud.fr/Labos/LPSN/cv/guillaume_eng.php?ID=381Search for more papers by this authorProf.Dr. Cyrille Kouklovsky, Prof.Dr. Cyrille Kouklovsky Université Paris-Sud and CNRS, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), UMR 8182, Laboratoire de Chimie des Procédés et Substances Naturelles, Bat. 410, 91405 Orsay (France) http://www.icmmo.u-psud.fr/Labos/LPSN/cv/guillaume_eng.php?ID=381Search for more papers by this authorDr. Guillaume Vincent, Corresponding Author Dr. Guillaume Vincent [email protected] Université Paris-Sud and CNRS, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), UMR 8182, Laboratoire de Chimie des Procédés et Substances Naturelles, Bat. 410, 91405 Orsay (France) http://www.icmmo.u-psud.fr/Labos/LPSN/cv/guillaume_eng.php?ID=381Université Paris-Sud and CNRS, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), UMR 8182, Laboratoire de Chimie des Procédés et Substances Naturelles, Bat. 410, 91405 Orsay (France) http://www.icmmo.u-psud.fr/Labos/LPSN/cv/guillaume_eng.php?ID=381Search for more papers by this author First published: 04 November 2012 https://doi.org/10.1002/anie.201206611Citations: 95 † We thank the CNRS and the Université Paris-Sud (Fellowship to R.B.) for financial support, and Didier Gori for HPLC analysis. 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 IRONic electrophilic indoles! The C3-regioselective hydroarylation of N-acetyl indoles with aromatic nucleophiles mediated by FeCl3 features a rare example of the electrophilic reactivity of the indole core in a Friedel–Crafts reaction. This indole umpolung allows us straightforward access to the tetracyclic benzofuroindoline motif found in the natural product diazonamide A, which is a potent antitumor agent. Supporting Information Detailed facts of importance to specialist readers are published as "Supporting Information". Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Filename Description anie_201206611_sm_miscellaneous_information.pdf5.3 MB miscellaneous_information 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 1aN. Lindquist, W. Fenical, G. D. Van Duyne, J. Cjardy, J. Am. Chem. Soc. 1991, 113, 2303–2304; 1bJ. Li, A. W. Burgett, L. Esser, C. Amezscusa, P. G. Harran, Angew. Chem. 2001, 113, 4906–4909; Angew. Chem. Int. Ed. 2001, 40, 4770–4773; 1cT.-S. Kam, S.-J. Tan, S.-W. Ng, K. Komiyama, Org. Lett. 2008, 10, 3749–3752; 1dQ.-X. Wu, M. S. Crews, M. Draskovic, J. Sohn, T. A. Johnson, K. Tenney, F. A. Valeriote, X.-J. Yao, L. F. Bjeldanes, P. Crews, Org. Lett. 2010, 12, 4458–4461. 2 2aG. Wang, L. Shang, A. W. G. Burgett, P. G. Harran, X. Wang, Proc. Natl. Acad. Sci. USA 2007, 104, 2068–2073; 2bN. S. Williams, A. W. G. Burgett, A. S. Atkins, X. Wang, P. G. Harran, S. L. McKnight, Proc. Natl. Acad. Sci. USA 2007, 104, 2074–2079. 3For a review, see: 3aM. Lachia, C. J. Moody, Nat. Prod. Rep. 2008, 25, 227–253; for representative examples, see: 3bK. C. Nicolaou, M. Bella, D. Y.-K. Chen, X. Huang, T. Ling, S. A. Snyder, Angew. Chem. 2002, 114, 3645–3649; Angew. Chem. Int. Ed. 2002, 41, 3495–3499; Angew. Chem. 2002, 114, 3645–3649; 3cK. C. Nicolaou, P. Bheema Rao, J. Hao, M. V. Reddy, G. Rassias, X. Huang, D. Y.-K. Chen, S. A. Snyder, Angew. Chem. 2003, 115, 1795–1800; Angew. Chem. Int. Ed. 2003, 42, 1753–1758; 3dC.-M. Cheung, F. W. Goldberg, P. Magnus, C. J. Russell, R. Turnbull, V. Lynch, J. Am. Chem. Soc. 2007, 129, 12320–12327; 3eC.-K. Mai, M. F. Sammons, T. Sammakia, Angew. Chem. 2010, 122, 2447–2450; Angew. Chem. Int. Ed. 2010, 49, 2397–2400; 3fR. R. Knowles, J. Carpenter, S. B. Blakey, A. Kayano, I. K. Mangion, C. J. Sinz, D. W. C. MacMillan, Chem. Sci. 2011, 2, 308–311; 3gW. Tian, L. Rao Chennamaneni, T. Suzuki, D. Y.-K. Chen, Eur. J. Org. Chem. 2011, 1027–1031. 4A. W. G. Burgett, Q. Li, Q. Wei, P. G. Harran, Angew. Chem. 2003, 115, 5111–5116; Angew. Chem. Int. Ed. 2003, 42, 4961–4966. 5For a low yielding intermolecular version, see: K. C. Nicolaou, S. M. Dalby, S. Li, T. Suzuki, D. Y.-K. Chen, Angew. Chem. 2009, 121, 7752–7756; Angew. Chem. Int. Ed. 2009, 48, 7616–7620. 6For selected examples of the regioselective synthesis of C3–aryl indoline derivatives, see: 6aS. Zhu, D. W. C. Mac Millan, J. Am. Chem. Soc. 2012, 134, 10815–10818; 6bK.-J. Wu, L.-X. Dai, S.-L. You, Org. Lett. 2012, 14, 3772–3775; 6cJ. Kim, M. Movassaghi, J. Am. Chem. Soc. 2011, 133, 14940–14943; 6dL. Furst, J. M. R. Narayanam, C. R. J. Stephenson, Angew. Chem. 2011, 123, 9829–9833; Angew. Chem. Int. Ed. 2011, 50, 9655–9659; 6eR. B. Bedford, N. Fey, M. F. Haddow, R. F. Sankey, Chem. Commun. 2011, 47, 3649–3651; 6fV. R. Espejo, X.-B. Li, J. D. Rainier, J. Am. Chem. Soc. 2010, 132, 8282–8284; 6gM. W. Boal, A. W. Schammel, N. K. Garg, Org. Lett. 2009, 11, 3458–3461; 6hK. Eastman, P. S. Baran, Tetrahedron 2009, 65, 3149–3154; 6iK. Matsumoto, H. Tokuyama, T. Fukuyama, Synlett 2007, 3137–3140; 6jS. P. Govek, L. E. Overman, J. Am. Chem. Soc. 2001, 123, 9468–9469; 6kF. Yamada, A. Goto, M. Somei, Heterocycles 2000, 53, 1255–1258. 7For selected examples of the hydroarylation of alkenes, see: 7aY. Kuninobu, T. Matsuki, K. Takai, J. Am. Chem. Soc. 2009, 131, 9914–9915; 7bJ. Kischel, I. Jovel, K. Mertins, A. Zapf, M. Beller, Org. Lett. 2006, 8, 19–22. 8M. Bandini, A. Eischholzer, Angew. Chem. 2009, 121, 9786–9824; Angew. Chem. Int. Ed. 2009, 48, 9608–9644. 9The addition of nucleophiles at the C2-position of indoles as the result of the preliminary activation of the C3-position by electrophiles is known; see: C. C. J. Loh, D. Enders, Angew. Chem. 2012, 124, 46–49; Angew. Chem. Int. Ed. 2012, 51, 46–48. 10Indoles substituted with electron-withdrawing groups at C3 can react with nucleophiles at C2; see: L. Wang, Y. Shao, Y. Liu, Org. Lett. 2012, 14, 3978–3981. 11For the generation of oxidized C3-substituted indole derivatives which are electrophilic at C3, see references [6c,f,i,k]. 12 12aK. Nishida, E. Yanase, S.-i. Nakatsuka, ITE Lett. Batteries New Technol. Med. 2006, 7, 59–62; 12bN. Tajima, T. Hayashi, S.-N. Nakatsuka, Tetrahedron Lett. 2000, 41, 1059–1062. 13For iron promoted C-H transformations, see: 13aC.-L. Sun, B.-J. Li, Z.-J. Shi, Chem. Rev. 2011, 111, 1293–1314; 13bK. Komeyama, K. Aihara, T. Kashira, K. Takaki, Chem. Lett. 2011, 40, 1254–1256. 14S. M. Bonesi, M. Fagnoni, Chem. Eur. J. 2010, 16, 13572–13589. 15K. Ding, Y. Wang, L. Zhang, Y. Wu, T. Matsuura, Tetrahedron 1996, 52, 1005–1010. 16CCDC 850422 (8 a), 850423 (3 g), and 850424 (16) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. 17For the formation of complexes between phenols and FeCl3, see: S. Banerjee, B. C. Haldar, Nature 1950, 165, 1012. 18T. Benkovics, I. A. Guzei, T. P. Yoon, Angew. Chem. 2010, 122, 9339–9343; Angew. Chem. Int. Ed. 2010, 49, 9153–9157. 19A. Goti, M. Romani, Tetrahedron Lett. 1994, 35, 6567–6570. 20 20aG. Vincent, Y. Chen, J. W. Lane, R. M. Williams, Heterocycles 2007, 72, 385–398; 20bX. Xu, X. Li, Org. Lett. 2009, 11, 1027–1029. 21MnO2 yields about 20 % of 3 a, whereas the Dess–Martin reagent did not afforded the expected product, 3 a. 22Benzofuroindoline 3 i (R4=I) was formed with good conversion, as observed in the crude NMR spectrum; however, we were not able to isolate it by flash column chromatography. 23No 3-arylchromenoindolines are reported in the literature, for 3-alkylchromenoindolines, see: 23aB. M. Trost, J. Quancard, J. Am. Chem. Soc. 2006, 128, 6314–6315; 23bS. L. Crawley, R. L. Funk, Org. Lett. 2003, 5, 3169–3172. 24Chromenoindoline 17 slowly rearranged to indole 20 in CDCl3 after 1,2 migration of the benzyl group from C3 to C2. For related examples of a 1,2 shift, see: 24aW. E. Noland, F. J. Baude, J. Org. Chem. 1966, 31, 3321–3337; 24bJ. Bergman, N. Eklund, Tetrahedron 1980, 36, 1445–1450. 25We speculate that the minor enantioerosion from pure (L)-proline has its origin in the preparation of indole 18. Citing Literature Volume51, Issue50December 7, 2012Pages 12546-12550 ReferencesRelatedInformation

Referência(s)