302 Sun, Hu, and Liu
ε), 398 (3.61), 496 (2.59), 528 (2.47), 565 (2.28), 619
(2.20). ESI+–MS (45 ev), m/z = 509.16 [M − H]−,
447.09 [M H 2CH3 2OH]−, 432.06 [M H CH2
compounds. This method is efficient and rapid us-
ing stoichiometric isobutylaldehyde, environmental
dioxygen, and catalytic Co(II)DPDME. Compared
with the recently reported methods in which the
Cu(II)TPP and Ru(III)TPP have been used as cata-
lysts, the possible mechanism is generally discussed,
which provides a new insight into the interaction
between metalloporphyrins and dioxygen plus alde-
hydes. In addition, these studies are useful for our
understanding of the natural intermediates involved
in metalloporphyrin-catalyzed reaction.
CH2COOH]−,
421.12
[M H CH3 CH2
CH2
COOH]−, 406.90 [M H 2CH3 CH2CH2COOH]−,
378.07[M H 4CH3 CH2CH2COOH]−.
Preparation of Deuteroporphyrin Dimethyl Ester
To the mixture of deuteroporphyrin (1.0 g, 1.96
mmol) and excess alcohol (0.30 mol) in a boiling
flask of 150 mL, concentrated H2SO4 (0.1 mL) was
added as catalyst at room temperature in an ul-
trasound bath having a frequency of 40 kHz. After
the addition, the mixture was irradiated by ultra-
sound for 0.5 h, and then extracted with CH2Cl2 (3 ×
100 mL). The organic layer was washed with water,
dried over anhydrous Na2SO4. After solvent removal,
the residue was further purified by column chro-
matography on silica gel (dichloromethane:ethyl ac-
etate = 10:1) to afford 0.9 g (1.67 mmol, 85.38%) of
deuteroporphyrins dimethyl ester as brick-red solid:
mp 224–225◦C. 1H NMR (500 MHz, CDCl3): δ (ppm)
= −3.87 (s, 2H), 3.30, 3.29, 3.27 (t, J = 7.25, 4H),
3.73, 3.75 (2s, 6H), 3.63–3.66 (4s, 12H), 4.41, 4.42,
4.44 (t, J = 7.25, 4H), 9.08, 9.09 (2s, 2H), 10.03,
10.07, 10.10, 10.13 (4s, 4H). IR (KBr, cm−1): 3400 (m,
REFERENCES
[1] Choudhary, D.; Paul, S.; Gupta, R.; Clark, J. H. Green
Chem 2006, 8, 479–482.
[2] Shibuya, M.; Osada, Y.; Sasano, Y.; Tomizawa, M.;
Iwabuchi, Y. J Am Chem Soc 2011, 133, 6497–6500.
[3] (a) Conte, M.; Miyamura, H.; Kobayashi, S.; Chechik,
V. J Am Chem Soc 2009, 131, 7189–7196. (b) Choud-
hary, V. R.; Dumbre, D. K. Catal Commun 2011, 13,
82–86.
[4] (a) Jiang, N.; Ragauskas, A. J. Tetrahedron Lett 2007,
48, 273–276. (b) Velusamy, S.; Punniyamurthy, T.
Org Lett 2004, 6, 217–219.
[5] (a) Karimi, B.; Zamani, A.; Abedi, S.; Clark, J. H.
Green Chem 2009, 11, 109–119. (b) Bianchini, C.;
Shen, P. K. Chem Rev 2009, 109, 4183–4206. (c)
Mifsud, M.; Parkhomenko, K. V.; Arends, I. W. C.
E. Tetrahedron 2010, 66, 1040–1044.
=
N H), 2900 (w), 1733 (s, C O), 1435 (m), 1361 (m),
1300 (w), 1235 (w), 1196 (m), 1165 (s, C O), 1125
(m), 1055 (w), 1016 (m), 970 (m), 894 (w), 845 (s).
[6] (a) Yamaguchi, K.; Mizuno, N. Angew Chem 2002,
114, 4720–2724. (b) Johnston, E. V.; Karlsson, E. A.;
˚
Tran, L. H.; Akermark, B.; Ba¨ckvall, J. E. Eur J Org
Chem 2010, 10, 1971–1976. (c) Arends, I. W. C. E.;
Kodama, T., Sheldon, R. A. Top Organomet Chem
2004, 11, 277–320.
Typical Procedure for Oxidation of Benzyl
Alcohols Using Dioxygen Catalyzed by
Co(II)DPDPME in the Presence of
Isobutylaldehyde
[7] (a) Furukawa, S.; Tamura, A.; Shishido, T.; Tera-
mura, K.; Tanaka T.; Appl Catal B 2011, 110, 216–
220. (b) Mao, J. P.; Deng, M. M.; Xue, Q. S.; Chen, L.;
Lu, Y. Catal Commun 2009, 10, 1376–1379.
[8] Karimi, B.; Biglari, A.; Clark, J. H.; Budarin, V. Angew
Chem, Int Ed 2007, 46, 7210–7213.
[9] Coleman, M. G.; Brown, A. N.; Bolton, B. A.; Guan,
H. Adv Synth Catal 2010, 352, 967–970.
[10] Marko´, I. E.; Giles, P. R.; Tsukazaki, M.; Chello´-
Regnaut, I.; Urch, C. J.; Brown, S. M. J Am Chem
Soc 1997, 119, 12661–12662.
[11] Rabe, K. S.; Gandubert, V. J.; Spengler, M.; Erkelenz,
M.; Niemeyer C. M. Anal Bioanal Chem, 2008, 392,
1059–1073.
[12] (a) Oh, N. Y.; Suh, Y.; Park, M. J.; Seo, M. S.; Kim,
J.; Nam, W. Angew Chem 2005, 117, 4307–4311. (b)
Korotchenko, V. N., Severinb, K.; Gagne´, M. R. Org
Biomol Chem 2008, 6, 1961–1965.
[13] Moghadam, M.; Tangestaninejad, S.; Mirkhani, V.;
Kargar, I. M. B. H. Bioorg Med Chem 2005, 13, 2901–
2905.
According to the reported procedure, the oxidation
of benzyl alcohol was carried out in a 50-mL flask
containing benzyl alcohol (1 mmol), Co(II)DPDME
(0.01 mmol), acetonitrile (6 mL), and isobutylalde-
hyde(3 mmol). The reaction mixture was stirred
at 60◦C for appropriated reaction time. Dioxygen
(1 atm) was bubbled through the solution. The reac-
tion was monitored via GC/MS analysis. After com-
pletion, the mixture was diluted with diethyl ether
and centrifuged to separate the catalyst. Then, the
product was analyzed by GC/MS, which can be eas-
ily identified by comparing the mass spectra data
library.
CONCLUSION
[14] (a) Rezaeifard, A.; Jafarpour, M.; Moghaddam, G. K.;
Amini, F. Bioorg Med Chem 2007, 15, 3097–3101. (b)
Rezaeifard, A.; Jafarpour, M.; Naeimi, A. Catal Com-
mun 2011, 16, 240–244. (c) Rezaeifard, A.; Jafarpour,
We have demonstrated the utility of the new proce-
dure for the oxidation of alcohols to the carbonyl
Heteroatom Chemistry DOI 10.1002/hc