M. Zhu et al. / Tetrahedron 64 (2008) 9239–9243
9243
Table 5
Oxidation of various alcohols catalyzed by complex 3 in the presence of O2/TEMPO
Entry
Substrate
CH2OH
Product
Conversion (%)
76.0
Selectivity (%)
100
Yielda (%)
CHO
CHO
37
76.0 (74.1)
76.8 (72.4)
60.7 (57.0)
MeO
Cl
MeO
Cl
CH2OH
38
39
76.8
60.7
100
100
CH2OH
CHO
Br
Br
40
41
61.2
71.0
100
100
61.2 (54.4)
71.0 (66.7)
CH2OH
CHO
CHO
O
O
CH2OH
CH2OH
CHO
42
43
6.3
3.1
100
100
6.3
3.1
OH
O
CH2OH
OH
44
45
CHO
3.2
2.4
100
100
3.2
2.4
O
OH
O
46
<0.1
100
d
The reaction conditions are the same as in Table 4.
a
The data in parenthesis are the isolated yields of the corresponding major products.
Chem. Soc. 2004, 126, 4112; (d) Lei, M.; Hu, R. J.; Wang, Y. G. Tetrahedron 2006, 62,
8928; (e) Qian, W. X.; Jin, E. L.; Bao, W. L.; Zhang, Y. M. Tetrahedron 2006, 62, 556.
3. (a) Ullman’s Encyclopedia of Industrial Chemistry, 6th ed.; Wiley-VCH: Weinheim,
2002; (b) Norman, R. O. C.; Coxon, J. M. Principles of Organic Synthesis, 3rd ed.;
Blackie Academic & Professional: London, 1993.
4. (a) Noyori, R.; Aoki, M.; Sato, K. Chem. Commun. 2003, 1977; (b) Velusamy, S.;
Ahamed, M.; Punniyamurthy, T. Org. Lett. 2004, 6, 4821; (c) Lounis, Z.; Riahi, A.;
Djafri, F.; Muzart, J. Appl. Catal. A: Gen. 2006, 309, 270; (d) Kato, C. N.; Hasegawa,
M.; Sato, T.; Inoue, T.; Mori, W. J. Catal. 2005, 230, 226.
5. (a) Jiang, N.; Ragauskas, A. J. Tetrahedron Lett. 2007, 48, 273; (b) Reddy, K. M.;
Balaraju, M.; Prasad, P. S. S.; Suranarayana, I.; Lingaiah, N. Catal. Lett. 2007, 119,
304; (c) Boitsov, S.; Songstad, J.; Muzart, J. J. Chem. Soc., Perkin Trans. 2 2001,
2318; (d) Gruttadauria, M.; Liotta, L. F.; Deganello, G.; Noto, R. Tetrahedron 2003,
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C. Chem. Commun. 2007, 4375.
TEMPO (0.18 mmol), NaOH (0.18 mmol), and O2 (0.1 MPa) were
stirred at 343 K in acetonitrile/water (6 mL/3 mL) for appropriate
time. The products were characterized by comparison with au-
thentic samples on a capillary gas chromatography (GC) equipped
with a column of DM-Wax (30 mꢁ0.25 mmꢁ1.0
mm) and a Flame
Ionization Detector (FID). The conversion and product selectivity
were calculated using cyclohexanone as the internal standard.
Purifications of the crude products by chromatography over silica
gel (hexane/AcOEt¼12/1 as eluent) gave analytically pure products.
Acknowledgements
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This work was supported by the NSFC (20473065, 20423002 and
20433030), the Key Project of Fujian Province (2005HZ01-3), the Re-
search Foundation for the Doctoral Program of Higher Education
(20050384011), and the Key Project of Chinese Ministry of Education
(106099).
References and notes
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