Communication
Organic & Biomolecular Chemistry
fluorescent indicator UV254, 0.2 mm) and visualized using 3 For two excellent reviews, see: (a) C. L. Allen and
2
54 nm UV light or iodine. Chemicals were purchased from
J. M. J. Williams, Chem. Soc. Rev., 2011, 40, 3405–3415;
(b) R. García-Álvarez, P. Crochet and V. Cadierno, Green
Chem., 2013, 15, 46–66.
Aldrich and were used without further purification unless
otherwise noted. All compounds were characterized by
NMR and C NMR. H spectra were recorded on Bruker AV 4 (a) X.-F. Wu, H. Neumann and M. Beller, Chem. Soc. Rev.,
3
at 282 MHz. GC was performed on an Agilent 6890 chromato-
graph with a 30 m HP5 column. All yields reported refer to iso-
lated yields. All the products are commercially available.
1
H
1
3
1
1
3
00 and AV 400 spectrometers. C NMR spectra were recorded
2011, 40, 4986–5009; (b) X.-F. Wu, H. Neumann and
M. Beller, Chem. Rev., 2012, 113, 1–35; (c) M. Beller and
X.-F. Wu, Transition Metal Catalyzed Carbonylation Reactions:
Carbonylative Activation of C-X Bonds, Springer, 2013.
5
(a) L. Cao, J. Ding, M. Gao, Z. Wang, J. Li and A. Wu, Org.
Lett., 2009, 11, 3810–3813; (b) J. Ding, L. Cao, J. Wang,
W. Xue, Y. Zhu and A. Wu, J. Chem. Res., 2011, 298–301;
(c) N. A. Angeles, F. Villavicencio, C. Guadarrama, D. Corona
and E. Cuevas-Yañez, J. Braz. Chem. Soc., 2010, 21, 905–908.
General procedure for the oxidative synthesis of primary
amides from acetophenones
Ammonia (25% in water; 1 mL) and acetophenones (1 mmol)
were added to a pressure tube equipped with a stirring bar.
2
Then, TBHP (70% in H O; 1.0 mL; 8 equiv.) and TBAI (20 mol%) 6 (a) X.-F. Wu, H. Neumann and M. Beller, Chem. – Eur. J.,
were added and the final solution was kept at 100 °C for 16 h.
The mixture was cooled to room temperature and the solvent
was removed under vacuum. The products obtained were puri-
fied by column chromatography (ethyl acetate–hexane = 1 : 2).
2010, 16, 9750–9753; (b) X.-F. Wu, H. Neumann and
M. Beller, Chem. – Asian J., 2010, 5, 2168–2172; (c) X.-F. Wu,
H. Neumann and M. Beller, Chem. – Eur. J., 2012, 18,
419–422; (d) X.-F. Wu, C. B. Bheeter, H. Neumann,
P. H. Dixneuf and M. Beller, Chem. Commun., 2012, 48,
General procedure for the oxidative synthesis of primary
amides from carbinols
12237–12239; (e) X.-F. Wu, M. Sharif, J.-B. Feng, H. Neumann,
A. Pews-Davtyan, P. Langer and M. Beller, Green Chem.,
2013, 15, 1956–1961; (f) M. Sharif, J.-L. Gong, P. Langer,
M. Beller and X.-F. Wu, Chem. Commun., 2014, 50, 4747–4750.
Ammonia (25% in water; 1 mL) and carbinols (1 mmol) were
added to a pressure tube equipped with a stirring bar. Then,
2
TBHP (70% in H O; 1.0 mL; 8 equiv.) and TBAI (20 mol%) 7 (a) M. Uyanik and K. Ishihara, ChemCatChem, 2012, 4, 177–185;
were added and the final solution was kept at 100 °C for 16 h.
The mixture was cooled to room temperature and the solvent
(b) X.-F. Wu, J.-L. Gong and X. Qi, Org. Biomol. Chem., 2014,
12, 5807–5817.
was removed under vacuum. The products obtained were puri- 8 For selected examples on using TBAI as the catalyst in
fied by column chromatography (ethyl acetate–hexane = 1 : 2).
oxidation reactions, see: (a) X. Li, X. Xu and C. Zhou, Chem.
Commun., 2012, 48, 12240–12242; (b) X. Li, X. Xu and
Y. Tang, Org. Biomol. Chem., 2013, 11, 1739–1742; (c) X. Li,
X. Xu, P. Hu, X. Xiao and C. Zhou, J. Org. Chem., 2013, 78,
Acknowledgements
7343–7348; (d) Y. Gao, Q. Song, G. Cheng and X. Cui, Org.
The authors thank the state of Mecklenburg-Vorpommern, the
Bundesministerium für Bildung und Forschung (BMBF) and
the Deutsche Forschungsgemeinschaft for financial support.
We also thank Dr C. Fischer, S. Schareina and Dr W. Baumann
for their excellent technical and analytical support.
Biomol. Chem., 2014, 12, 1044–1047; (e) J. Zhang, J. Jiang,
Y. Li and X. Wan, J. Org. Chem., 2013, 78, 11366–11372;
(
f) L.-T. Li, J. Huang, H.-Y. Li, L.-J. Wen, P. Wang and
B. Wang, Chem. Commun., 2012, 48, 5187–5189; (g) L.-T. Li,
H.-Y. Li, L.-J. Xing, L.-J. Wen, P. Wang and B. Wang, Org.
Biomol. Chem., 2012, 10, 9519–9522; (h) H. Li, J. Xie, Q. Xue,
Y. Cheng and C. Zhu, Tetrahedron Lett., 2012, 53, 6479–6482;
Notes and references
(i) K. Xu, Y. Hu, S. Zhang, Z. Zha and Z. Wang, Chem. – Eur.
1
(a) Metal-Catalyzed reactions in water, ed. P. H. Dixneuf and
V. Cadierno, Wiley-VCH, 2013; (b) R. Noyori, Chem.
Commun., 2005, 1807–1811; (c) M.-O. Simon and C.-J. Li,
Chem. Soc. Rev., 2012, 41, 1415–1427; (d) X. Han and
M. Poliakoff, Chem. Soc. Rev., 2012, 41, 1428–1436;
J., 2012, 18, 9793–9797; ( j) G. Wang, Q.-Y. Yu, S.-Y. Chen and
X.-Q. Yu, Org. Biomol. Chem., 2014, 12, 414–417;
(k) W.-P. Mai, G. Song, J.-W. Yuan, L.-R. Yang, G.-C. Sun,
Y.-M. Xiao, P. Mao and L.-B. Qu, RSC Adv., 2013, 3, 3869–
3872; (l) L. Ma, X. Wang, W. Yu and B. Han, Chem.
Commun., 2011, 47, 11333–11335; (m) Q. Xue, J. Xie, H. Li,
Y. Cheng and C. Zhu, Chem. Commun., 2013, 49, 3700–3702;
(n) J. Feng, S. Liang, S.-Y. Chen, J. Zhang, S.-S. Fu and
X.-Q. Yu, Adv. Synth. Catal., 2012, 354, 1287–1292;
(o) L. Chen, E. Shi, Z. Liu, S. Chen, W. Wei, H. Li, K. Xu and
X. Wan, Chem. – Eur. J., 2011, 17, 4085–4089; (p) J. Zhao,
P. Li, C. Xia and F. Li, Chem. Commun., 2014, 50, 4751–4754.
(e) R. B. N. Baig and R. S. Varma, Chem. Soc. Rev., 2012, 41,
1
559–1584.
2
(a) F. Matsuda, Chemtech, 1977, 7, 306; (b) C. E. Mabermann,
in Encyclopedia of Chemical Technology, ed. J. I. Kroschwitz,
Wiley, New York, 1991, vol. 1, pp. 251–266; (c) D. Lipp, in
Encyclopedia of Chemical Technology, ed. J. I. Kroschitz,
Wiley, New York, 1991, vol. 1, pp. 266–287; (d) R. Opsahl, in
Encyclopedia of Chemical Technology, ed. J. I. Kroschwitz, 9 Y.-Z. Hui, Y.-H. Cai and X.-E. Chen, Acta. Chim. Sin., 1988, 6,
Wiley, New York, 1991, vol. 2, pp. 346–356. 91–94.
6362 | Org. Biomol. Chem., 2014, 12, 6359–6362
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