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Synthesis 2014; 46(15): 2057-2064
DOI: 10.1055/s-0033-1338622
DOI: 10.1055/s-0033-1338622
paper
Decarboxylative Hydroamination of 3-Arylpropiolic Acids with N-Heterocycles under Transition-Metal-Free Conditions
Further Information
Publication History
Received: 28 February 2014
Accepted after revision: 25 March 2014
Publication Date:
23 April 2014 (online)

Abstract
A decarboxylative hydroamination cascade reaction of 3-arylpropiolic acids with N-heterocycles under transition-metal-free conditions was developed. 3-Arylpropiolic acids were found to react smoothly with a range of N-heterocycles under the effect of t-BuOK to afford N-vinyl heterocycles in moderate to excellent yields. This reaction represents the first decarboxylative hydroamination of 3-arylpropiolic acids without the aid of a transition-metal catalyst.
Key words
alkynes - decarboxylation - hydroamination - N-vinyl heterocycle - potassium tert-butoxideSupporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synthesis.
- Supporting Information
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References
- 1a Gooβen LJ, Rodríguez N, Gooβen K. Angew. Chem. Int. Ed. 2008; 47: 3100
- 1b Baudoin O. Angew. Chem. Int. Ed. 2007; 46: 1373
- 1c You S.-L, Dai L.-X. Angew. Chem. Int. Ed. 2006; 45: 5246
- 1d Tunge J, Burger AE. Eur. J. Org. Chem. 2005; 1715
- 2a Rayabarapu DK, Tung JA. J. Am. Chem. Soc. 2005; 127: 13510
- 2b Zhang W.-W, Zhang X.-G, Li J.-H. J. Org. Chem. 2010; 75: 5259
- 2c Torregrosa RR, Ariyarathna PY, Chattopadhyay K, Tunge JA. J. Am. Chem. Soc. 2010; 132: 9280
- 2d Choe J, Yang J, Park K, Palani T, Lee S. Tetrahedron Lett. 2012; 53: 6908
- 2e Moon J, Jang M, Lee S. J. Org. Chem. 2009; 74: 1403
- 2f Wang ZY, Ding QP, He XD, Wu J. Tetrahedron 2009; 65: 4635
- 2g Wang ZY, Ding QP, He XD, Wu J. Org. Biomol. Chem. 2009; 7: 863
- 2h Gooβen LJ, Zimmermann B, Knauber T. Angew. Chem. Int. Ed. 2008; 47: 7103
- 2i Gooβen L, Rudolphi JF, Oppel C, Rodríguez N. Angew. Chem. Int. Ed. 2008; 47: 3043
- 2j Gooβen LJ, Rodríguez N, Linder C. J. Am. Chem. Soc. 2008; 130: 15248
- 2k Wang C, Tunge JA. J. Am. Chem. Soc. 2008; 130: 8118
- 2l Moon J, Jeong M, Nam H, Ju J, Moon JH, Jung HM, Lee S. Org. Lett. 2008; 10: 945
- 2m Zhao D, Gao C, Su X, He Y, You J, Xue Y. Chem. Commun. 2010; 46: 9049
- 2n Qu X, Li T, Sun P, Zhu Y, Yang H, Mao J. Org. Biomol. Chem. 2011; 9: 6938
- 2o Feng C, Loh T.-P. Chem. Commun. 2010; 46: 4779
- 2p Yu M, Pan D, Jia W, Chen W, Jiao N. Tetrahedron Lett. 2010; 51: 1287
- 2q Park J, Park E, Kim A, Park S.-A, Lee Y, Chi K.-W, Jung YH, Kim IS. J. Org. Chem. 2011; 76: 2214
- 2r Kim Y, Park A, Park K, Lee S. Tetrahedron Lett. 2011; 52: 1766
- 2s Ranjit R, Duan Z, Zhang PX, Liu X. Org. Lett. 2010; 12: 4134
- 2t Jia W, Jiao N. Org. Lett. 2010; 12: 2000
- 2u Hu J, Zhao N, Yang B, Wang G, Guo LN, Liang YM, Yang SD. Chem. Eur. J. 2011; 17: 5516
- 2v Priebbenow DL, Becker P, Bolm C. Org. Lett. 2013; 15: 6155
- 3a Reychler A. Bull. Soc. Chim. Fr. 1897; 515
- 3b Gattermann L. Justus Liebigs Ann. Chem. 1906; 347: 353
- 4a Shirakawa E, Watabe R, Murakami T, Hayashi T. Chem. Commun. 2013; 49: 5219
- 4b Shirakawa E, Hayashi Y, Itoh K, Watabe R, Uchiyama N, Konagaya W, Masui S, Hayashi T. Angew. Chem. Int. Ed. 2012; 51: 218
- 5a Ross WJ, Jamieson WB, McCowen MC. J. Med. Chem. 1973; 16: 347
- 5b Hamada Y, Shinomoto S, Yamada I, Koike H. EP 162359, 1985 , Chem. Abstr. 1986, 104, 168465v.
- 5c Cockerrill AF, Rackham DM, Franklin NC, Norman C. J. Chem. Soc., Perkin Trans. 2 1973; 509
- 5d Gist-Brocades NV. NL 8005204, 1982 , Chem. Abstr. 1982, 100, 492276.
- 5e Kurdaziel K, Glowiak T. J. Coord. Chem. 2002; 55: 327
- 5f Mano N, Kim Y, Zhang HH, Heller A. J. Am. Chem. Soc. 2002; 124: 6480
- 5g Branowska D. Synthesis 2003; 2096
- 5h Beghdadi S, Miladi IA, Addis D, Romdhane HB, Bernard J, Drockenmuller E. Polym. Chem. 2012; 3: 1680
- 6 Extra-pure t-BuOK (sublimed grade, 99.99% trace metals basis) was purchased from Sigma–Aldrich.
- 7 Phenylacetylene was found to be labile in the presence of t-BuOK because no phenylacetylene was detected by GC under the same reaction conditions after 24 h.
- 8 No product was isolated when t-BuOK (2.2 equiv) was used, probably due to the instability of phenylacetylene in the presence of excess t-BuOK.
For selected reviews, see:
For sp–sp3 bond formation, see:
For sp–sp2 bond formation, see:
For sp–sp bond formation, see:
For sp–heteroatom bond formation, see:
For recent developments in cross-coupling reactions under transition-metal-free conditions, see: