Á. Kiss, Z. Hell / Tetrahedron Letters 52 (2011) 6021–6023
6023
Tetrahedron Lett. 2000, 41, 4845–4849; (j) Villain, G.; Kalck, P.; Gaset, A.
Tetrahedron Lett. 1980, 21, 2901–2904; (k) Maffioli, S. I.; Marzorati, E.; Marazzi,
A. Org. Lett. 2005, 7, 5237–5239; (l) Takaya, H.; Yoshida, K.; Isozaki, K.; Terai, H.;
Murahashi, S.-I. Angew. Chem., Int. Ed. 2003, 42, 3302–3304; (m) Ghaffar, T.;
Parkins, A. W. Tetrahedron Lett. 1995, 36, 8657–8660; (n) Jiang, X.-B.; Minnaard,
A. J.; Feringa, B. L.; de Vries, J. G. J. Org. Chem. 2004, 69, 2327–2331; (o) North, M.;
Parkins, A. W.; Shariff, A. N. Tetrahedron Lett. 2004, 45, 7625–7627.
supported on 4 Å molecular sieves proved to be a good and recycla-
ble catalyst. The catalyst could be easily prepared from the com-
mercially available MS-4 Å by impregnation with copper salt, the
experimental and work-up procedure was very simple. A further
advantage of our method is that it can be used with the compounds
having functional groups (e.g., ester) sensitive to conventional
hydrolytic methods.
3. Kim, H. S.; Kim, S. H.; Kim, J. N. Tetrahedron Lett. 2009, 50, 1717–1719.
4. Kim, H. S.; Kim, S. H.; Kim, J. N. Tetrahedron Lett. 2009, 50, 2973–2975.
5. Kiss, Á.; Hell, Z.; Pirault-Roy, L.; Gener-Batonneau, I.; Clacens, J.-M.; Pouilloux, Y.
Tetrahedron, submitted.
Acknowledgments
6. Preparation of the catalysts: 4 Å molecular sieves (MS-4 Å) were impregnated
with the corresponding metal salt (CuCl2Á2H2O, Na2PdCl4) as follows: 1 mmol of
the salts was dissolved in 100 ml of deionised H2O and stirred with 1 g of MS-4 Å
at room temperature for 6 h. The solid was filtered, washed with deionised H2O
and acetone, and dried in an oven at 150 °C for 1 h.
The authors are grateful to Chinoin Pharmaceutical and Chem-
ical Works Ltd., a member of the Sanofi-Aventis Group for the tech-
nical support and Á.K. for financial support.
7. A typical reaction was carried out in a 10 mL flask. Benzonitrile (2 mmol), CuII-
4 Å (0.2 g), acetaldoxime (6 mmol) and MeOH (4 mL) were stirred at 65 °C for
4 h. The solid was filtered, washed with MeOH and the filtrate evaporated. The
residue was subjected to GC-MS analysis and NMR spectroscopy. The filtered
catalyst can be recycled after drying at about 150 °C for 1 h.
References and notes
1. (a) Larock, R. C. Comprehensive Organic Transformations, second ed.; Wiley-VCH:
New York, 1999. p. 1988; (b) Beckwith, A. L. J. In The Chemistry of Amides
Synthesis of Amides; Zabicky, J., Ed.; Interscience: New York, 1970; p 73; (c)
Sydner, H. R.; Elston, C. T. J. Am. Chem. Soc. 1954, 76, 3039–3040; (d) Hauser, C.
R.; Eby, C. J. J. Am. Chem. Soc. 1957, 79, 725–727; (e) Wilgus, C. P.; Downing, S.;
Molitor, E.; Bains, S.; Pagni, R. M.; Kabalka, G. W. Tetrahedron Lett. 1995, 36,
3469–3472; (f) Basu, M. K.; Luo, F.-T. Tetrahedron Lett. 1998, 39, 3005–3006; (g)
McMaster, L.; Langreck, F. B. J. Am. Chem. Soc. 1917, 39, 103–109; (h) Kornblum,
N.; Singaram, S. J. Org. Chem. 1979, 44, 4727–4729; (i) Katritzky, A. R.; Pilarski,
B.; Urogdi, L. Synthesis 1989, 949–950.
2. (a) Kim, J. H.; Britten, J.; Chin, J. J. Am. Chem. Soc. 1993, 115, 3618–3622; (b) Chin,
J.; Kim, J. H. Angew. Chem., Int. Ed. Engl. 1990, 29, 523–525; (c) Breno, K. L.; Pluth,
M. D.; Tyler, D. R. Organometallics 2003, 22, 1203–1211; (d) Murahashi, S.-I.;
Sasao, S.; Saito, E.; Naota, T. J. Org. Chem. 1992, 57, 2521–2523; (e) Fung, W. K.;
Huang, X.; Man, M. L.; Ng, S. M.; Hung, M. Y.; Lin, Z.; Lau, C. P. J. Am. Chem. Soc.
2003, 125, 11539–11544; (f) Yamaguchi, K.; Matsushita, M.; Mizuno, N. Angew.
Chem., Int. Ed. 2004, 43, 1576–1580; (g) Leung, C. W.; Zheng, W.; Zhou, Z.; Lin, Z.;
Lau, C. P. Organometallics 2008, 27, 4957–4969; (h) Goto, A.; Endo, K.; Saito, S.
Angew. Chem., Int. Ed. 2008, 47, 3607–3609; (i) Djoman, M. C. K.-B.; Ajjou, A. N.
8. GC–MS spectra were recorded on
a
Shimadzu GC-2010, GC–MS QP2010S
m, temperature
instrument, column: HP-5MS, 30 m  0.25 mm  0.25
l
program: 40 °C (10 min) ? 10 °C/min ? 300 °C (26 min). Dodecane was used
as internal standard.
Representative examples: (4-Chlorophenyl)-acetamide (Table 4, entry 6): white
solid, 1H NMR (300 MHz, DMSO-d6) d (ppm): 3.34 (s, 2H, CH2), 6.87 (br s, 1H,
NH2), 7.26 (d, 2H, ArH), 7.31 (d, 2H, ArH), 7.45 (br s, 1H, NH2). GC: tR: 25.06 min.
MS m/z (%): 169(M+, 20), 126(75), 125(70), 91(100), 63(25), 44(55).
Cinnamamide (Table 4, entry 7): white solid, 1H NMR (300 MHz, DMSO-d6) d
(ppm): 6.63 (d, 1H, @CH–), 7.12 (br s, 1H, NH2), 7.38–7.44 (m, 4H, ArH, @CH–),
7.56–7.57 (m, 3H, ArH, NH2). GC: tR: 25.48 min. MS m/z (%): 147 (M+, 100),
131(45), 103(65), 91(20), 77(45), 51(30).
1-(3,4-Dimethoxyphenyl)-propan-2-oneoxime: mixture of E/Z isomers (74:26), 1
H
NMR (300 MHz, CDCl3) d (ppm): 1.795 (s, 3H, CH3, Z isomer), 1.809 (s, 3H, CH3, E
isomer), 3.42 (s, 2H, CH2, E isomer), 3.67 (s, 2H, CH2, Z isomer), 3.85 (s, 6H,
OCH3), 6.71-6.82 (m, 3H, ArH), 8.27 (br s, 1H, @N–OH). GC: tR: 26.73 min. MS m/
z(%): 209(M+, 80), 192(15), 176(20), 161(40), 151(100), 137(30), 107(35), 91(20),
77(20), 65(20).