Direct Catalytic Formation of Primary and Tertiary Amides from Non-Activated Carboxylic Acids
employed as catalysts for the formation of all classes
of amides.
[4] J. S. Carey, D. Laffan, C. Thomson, M. T. Williams Org.
Biomol. Chem. 2006, 4, 2337–2347.
[
5] D. J. C. Constable, P. J. Dunn, J. D. Hayler, G. R. Hum-
phrey, J. L. Leazer Jr, R. J. Linderman, K. Lorenz, J.
Manley, B. A. Pearlman, A. Wells, A. Zaksh, T. Y.
Zhang, Green Chem. 2007, 9, 411–420.
Experimental Section
[
6] a) H. Charville, D. Jackson, G. Hodges, A. Whiting,
Chem. Commun. 2010, 46, 1813–1823; b) R. M. Al-
Zoubi, O. Marion, D. G. Hall, Angew. Chem. 2008, 120,
Typical Procedure for the Formation of Primary
Amides Catalyzed by ZrCl4
2
918–2921; Angew. Chem. Int. Ed. 2008, 47, 2876–2879;
An oven-dried 15-mL Ace pressure tube with a stirring bar
was charged with the carboxylic acid (1.0 mmol), molecular
sieves 4 ꢁ (0.5 g), ZrCl4 (0.2 mmol, 0.0466 g), ammonium
carbamate (3.0 mmol, 0.234 g) and dry toluene (2.5 mL)
under a nitrogen atmosphere. The pressure tube was sealed
and put in a preheated oil bath. The mixture was stirred at
c) K. Arnold, B. Davies, D. Hꢃrault, A. Whiting,
Angew. Chem. 2008, 120, 2713–2716; Angew. Chem.
Int. Ed. 2008, 47, 2673–2676; d) T. Maki, K. Ishihara, H
Yamamoto, Tetrahedron 2007, 63, 8645–8657; e) K. Ishi-
hara, S. Ohara, H. Yamamoto, J. Org. Chem. 1996, 61,
4
196–4197; f) K. Arnold, A. S. Batsanov, B. Davies, A.
1
208C for 24 h and then cooled to room temperature. The
TM
Whiting, Green Chem. 2008, 10, 124–134; g) K. Arnold,
B. Davies, R. L. Giles, C. Grosjean, G. E. Smith, A.
Whiting, Adv. Synth. Catal. 2006, 348, 813–820; h) T.
Maki, K. Ishihara, H. Yamamoto, Org. Lett. 2006, 8,
reaction mixture was passed through a plug of Celite (4ꢂ
cm) eluted with 200 mL EtOAc. The solvent was removed
4
under reduced pressure affording in most cases the analyti-
cally pure product.
1
431–1434; i) P. Starkov, T. D. Sheppard, Org. Biomol.
Chem. 2011 9##, 1320–1323; j) K. Ishihara, Tetrahedron
009, 65, 1085–1109; k) C. Grosjean, J. Parker, C.
Typical Procedure for the Formation of N,N-
Dimethylamides Catalyzed by ZrCl4
2
Thirsk, A. R. Wright, Org. Process Res. Dev. 2012, 16,
An oven-dried 15-mL Ace pressure tube with a stirring bar
was charged with the carboxylic acid (1.0 mmol), molecular
781–789.
[7] a) R. V. Ulijn, B. BaragaÇa, P. J. Hallning, S. L. Flitsch,
J. Am. Chem. Soc. 2002, 124, 10988–10989; b) M. J. J.
Litjens, A. J. J. Straathof, J. A. Jongejan and J. J. Heij-
nen, Tetrahedron 1999, 55, 12411–12418; c) F. Van
Rantwijk, M. A. P. J. Hacking, R. A. Sheldon, Monatsh.
Chem. 2000, 131, 549–569.
[8] a) L. Y. Shteinberg, S. A. Kondratov, S. M. Shein, Zhur.
Organ. Khim. 1988, 24, 1968–1972; b) L. Y. Shteinberg,
S. A. Kondratov, S. M. Shein, Zhur. Organ. Khim. 1989,
sieves 4 ꢁ (0.5 g), ZrCl (0.2 mmol, 0.0466 g), dimethylam-
4
monium dimethylcarbamate (2.0 mmol, 0.268 g) and dry tol-
uene (2.5 mL) under a nitrogen atmosphere. The pressure
tube was sealed and put in a preheated oil bath. The mix-
ture was stirred at 1208C for 24 h and then cooled to room
temperature. The reaction mixture was passed through
a plug of silica (4ꢂ4 cm) eluted with 100 mL EtOAc:Et N
3
(
200:1). The solvent was removed under reduced pressure
affording in most cases the analytically pure product.
2
5, 1945–1949; c) ꢁ. Nordahl, R. Carlson, Acta Chem.
Scand. B 1988, 42, 28–34; d) P. S. Chaudhari, S. D.
Salim, R. V. Sawant, K. G. Akamanchi, Green Chem.
2
010, 12, 1707–1710; e) F. Tamaddon, F. Aboee, A.
Acknowledgements
Nasiri, Catal. Commun. 2011, 16, 194–197; f) M. Hos-
seini-Sarvari, E. Sodagar, M. M. Doroodmand, J. Org.
Chem. 2011, 76, 2853–2859.
We are grateful for financial support from the Swedish Re-
search Council, the Carl Trygger Foundation, the K & A Wal-
lenberg Foundation, and the Royal Swedish Academy of Sci-
ence.
[
9] C. L. Allen, A. R. Chhatwal, J. M. J. Williams Chem.
Commun. 2012, 48, 666–668.
[
[
10] H. Lundberg, F. Tinnis, H. Adolfsson, Chem. Eur. J.
012, 18, 3822–3826.
11] a) S. T. Chen, S. H. Wu, K. T. Wang, Synthesis 1989, 37–
2
3
1
8; b) W. Wang, J. S. McMurray, Tetrahedron Lett.
999, 40, 2501–2504; c) M. A. Bailꢃn, R. Chinchilla,
References
D. J. Dodsworth, C. Nꢄjera Tetrahedron Lett. 2000, 41,
9809–9813; d) K. S. Lee, K. D. Kim, Synth. Commun.
2011, 41, 3497–3500; e) K. J. Merchant Tetrahedron
Lett. 2000, 41, 3747–3749; f) V. Cadierno, J. Dꢅez, J.
Francos, J. Gimeno, Chem. Eur. J. 2010, 16, 9808–9817.
[
1] A. K. Ghose, V. N. Viswanadhan, J. J. Wendoloski, J.
Comb. Chem. 1999, 1, 55–68.
[2] a) L . Perreux, A. Loupy, F. Volatron, Tetrahedron
2
002, 58, 2155–2162; b) E. Gelens, L. Smeets,
L. A. J. M. Sliedregt, B. J. Van Steen, C. G. Kruse, R.
Leurs, R. V. A. Orru, Tetrahedron Lett. 2005, 46, 3751–
[12] a) C. Gunanathan, Y. Ben-David, D. Milstein, Science
2007, 317, 790–792; b) T. Zweifel, J.-V. Naubron, H.
Grꢆtzmacher, Angew. Chem. 2009, 121, 567–571;
Angew. Chem. Int. Ed. 2009, 48, 559–563; c) Y. Wang,
D. Zhu, L. Tang, S. Wang, Z. Wang, Angew. Chem.
2011, 123, 9079–9083; Angew. Chem. Int. Ed. 2011, 50,
8917–8921; d) J.-F. Soul, H. Miyamura, S. Kobayashi, J.
Am. Chem. Soc. 2011, 133, 18550–18553; e) K. Yama-
guchi, H. Kobayashi, T. Oishi, N. Mizuno Angew.
3
754; c) X.-J. Wang, Q. Yang, F. Liu, Q.-D. You, Synth.
Commun. 2008, 38, 1028–1035; d) L. J. Gooßen, D. M.
Ohlmann, P. P. Lange, Synthesis 2009, 160–164; e) H.
Charville, D. A. Jackson, G. Hodges, A. Whiting, M. R.
Wilson, Eur. J. Org. Chem. 2011, 5981–5990.
[
3] a) S. Han, Y. Kim, Tetrahedron 2004, 60, 2447–2467;
b) E. Valeur, M. Bradley, Chem. Soc. Rev. 2009, 38,
6
06–631.
Adv. Synth. Catal. 0000, 000, 0 – 0
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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