Subscribe to RSS
DOI: 10.1055/s-0035-1561305
Revisiting the Gold-Catalyzed Dimerization of 2-Ethynylanilines: A Room-Temperature and Silver-Free Protocol for the Synthesis of Multifunctional Quinolines
Publication History
Received: 11 October 2015
Accepted after revision: 02 December 2015
Publication Date:
07 January 2016 (online)
Dedicated to Professors Vèronique Michelet and Virginie Ratovelomanana-Vidal with friendship and respect for their contributions to transition-metal catalysis.
Abstract
A room temperature and silver-free protocol for the formation of quinolines from 2-ethynylanilines through a dimerization event was achieved using a dinuclear gold catalyst, Au2(BIPHEP)(NTf2)2. The reaction is inherently modular, allowing for the incorporation of peripheral substituents at any site of the quinoline product. The reaction is readily applied to other heterocyles also as exemplified by the preparation of naphthyridines. Competition reactions to determine the reactivity of dissimilar alkynes demonstrated that the product ratio of dimerization vs intermolecular addition is rather dependent on the electronic nature of aryl substituent on the alkynes. However, control experiments with substrates possessing internal alkynes resulted in cycloisomerization instead of expected dimerization, which is indicative of possible steric influence of the alkyne terminus in the reaction outcome.
Key words
2-ethynylanilines - dimerization - quinolines - atom-economy - dinuclear gold complex - silver-free approach - competition reactionsSupporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0035-1561305.
- Supporting Information
-
References
- 1a Dorel R, Echavarren AM. Chem. Rev. 2015; 115: 9028
- 1b Jiménez-Núñez E, Echavarren A. Chem. Commun. 2007; 333
- 2a Marion N, Nolan SP. Chem. Soc. Rev. 2008; 37: 1776
- 2b Nolan SP. Acc. Chem. Res. 2011; 44: 91
- 2c Muñoz MP, Adrio J, Carretero JC, Echavarren AM. Organometallics 2005; 24: 1293
- 2d Hashmi AS. K, Bührle M. Aldrichimica Acta 2010; 43: 27
- 3a Jia M, Bandini M. ACS Catal. 2015; 5: 1638
- 3b Lu Z, Han J, Hammond GB, Xu B. Org. Lett. 2015; 17: 4534
- 4 Wang W, Hammond G, Xu B. J. Am. Chem. Soc. 2012; 134: 5697
- 5 Gorin DJ, Sherry BD, Toste FD. Chem. Rev. 2008; 108: 3351
- 6a de Frémont P, Scott NM, Stevens ED, Nolan SP. Organometallics 2005; 24: 2411
- 6b Gu P, Xu Q, Shi M. Tetrahedron Lett. 2014; 55: 577
- 7a Hashmi AS. K, Lothschütz C, Böhling C, Hengst T, Hubbert C, Rominger F. Adv. Synth. Catal. 2010; 352: 3001
-
7b Hashmi AS. K, Lothschütz C, Graf K, Haffner T, Schuster A, Rominger F. Adv. Synth. Catal. 2011; 353: 1407
- 8 Jaimes MC. B, Böhling CR. N, Serrano-Becerra JM, Hashmi AS. K. Angew. Chem. Int. Ed. 2013; 52: 7963
-
9 Gaillard S, Cazin CS. J, Nolan SP. Acc. Chem. Res. 2012; 45: 778
- 10a Sakai N, Annaka K, Konakahara T. J. Org. Chem. 2006; 71: 3653
- 10b Sakai N, Annaka K, Fujita A, Sato A, Konakahara T. J. Org. Chem. 2008; 73: 4160
- 11a Praveen C, Jegatheesan S, Perumal PT. Synlett 2009; 2795
- 11b Praveen C, Kiruthiga P, Perumal PT. Synlett 2009; 1990
- 11c Praveen C, Kalyanasundaram A, Perumal PT. Synlett 2010; 777
- 11d Praveen C, Sagayaraj YW, Perumal PT. Tetrahedron Lett. 2009; 50: 644
- 11e Praveen C, Karthikeyan K, Perumal PT. Tetrahedron 2009; 65: 9244
- 11f Praveen C, Perumal PT. Synlett 2011; 521
- 11g Praveen C, Ayyanar A, Perumal PT. Bioorg. Med. Chem. Lett. 2011; 21: 4170
- 11h Praveen C, Perumal PT. Chin. J. Catal. 2016; 37 in press; DOI: 10.1016/S1872-2067(15)60994-9
- 12a Chen YL, Fang KC, Sheu JY, Hsu SL, Tzeng CC. J. Med. Chem. 2001; 44: 2374
- 12b Michael JP. Nat. Prod. Rep. 2007; 24: 223
- 13 Shelton PA, Hilliard CR, Swindling M, McElwee-White L. ARKIVOC 2010; viii: 160
- 14 Ezquerra J, Pedregal C, Lamas C. J. Org. Chem. 1996; 61: 5804
- 15 Sonogashira K, Tohda Y, Hagihara N. Tetrahedron Lett. 1975; 16: 4467
- 16 Koradin C, Dohle W, Rodriguez AL, Schmid B, Knochel P. Tetrahedron 2003; 59: 1571
- 17a Miyazaki Y, Kobayashi S. J. Comb. Chem. 2008; 10: 355
- 17b Ambrogio I, Arcadi A, Cacchi S, Fabrizi G, Marinelli F. Synlett 2007; 1775
- 17c Alfonsi M, Arcadi A, Aschi M, Bianchi G, Marinelli F. J. Org. Chem. 2005; 70: 2265
- 17d Nakamura I, Yamagishi U, Song D, Konta S, Yamamoto Y. Angew. Chem. Int. Ed. 2007; 46: 2284
- 18 Mézailles N, Richard L, Gagosz F. Org. Lett. 2005; 7: 4133
- 19 Hashmi AS. K, Blanco MC. Eur. J. Org. Chem. 2006; 4340
- 20a Uson R, Laguna A, Castrillo MV. Synth. React. Inorg. Met.-Org. Chem. 1979; 9: 317
- 20b Bayler A, Bauer A, Schmidbaur H. Chem. Ber./Recl. 1997; 130: 115
- 21 Bandini M, Monari M, Romaniello A, Tragni M. Chem. Eur. J. 2010; 12: 14272
- 22 Widenhoefer RA, Han X. Eur. J. Org. Chem. 2006; 4555
- 23 Roma G, Braccio MD, Grossi G, Mattioli F, Ghia M. Eur. J. Med. Chem. 2000; 1021
- 24 Pearson SE, Nandan S. Synthesis 2005; 2503
- 25 Kozlov NG, Basalaeva LI. Russ. J. Org. Chem. 2003; 39: 718