B. Zhang et al. / Tetrahedron 69 (2013) 2033e2037
2037
(0.15e0.2 mm). The developed chromatography was analyzed by
Supplementary data
UV lamp (254 nm). Melting points were measured on a RY-I ap-
paratus and uncorrected. Nuclear magnetic resonance (NMR)
spectra were recorded on a Bruker AV 400 spectrometer at
400 MHz (1H NMR) and 100 MHz (13C NMR) or a Bruker AV 300
spectrometer at 300 MHz (1H NMR) and 75 MHz (13C NMR).
Supplementary data related to this article can be found at http://
References and notes
Chemical shifts (d values) were reported in parts per million down
field from internal Me4Si (1H and 13C NMR). High Resolution Mass
Spectra (HRMS) were recorded on Varian IonSpec FT-ICR mass
spectrometer with ESI source. FT-IR spectra were recorded with
a Nicolet MAGNA-560 infrared spectrometer. Gas chromatography
(GC) analysis was conducted on a Hewlett Packard Model HP 6890
Series chromatography equipped with FID detectors using a HP-5
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62, 2439e2463; (d) Labinger, J. A.; Bercaw, J. E. Nature 2002, 417, 507e514.
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2. Modern Oxidation Methods; Backvall, J.-E., Ed.; WILEY-VCH: Weinheim, 2010.
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column (30 mꢁ0.32 mmꢁ0.25
mm).
4.2. A typical procedure for copper-catalyzed benzylic
oxidation
4. (a) Yadav, S.; Yadav, R. S. S.; Yadava, S.; Yadav, K. D. S. Catal. Commun. 2011, 12,
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Caution! Peroxy compounds present a serious detonation haz-
ard. While peresters are not as reactive as peracids, it is recom-
mended that the preparation and all reactions of peresters should
be carried out with protection.
€
Backvall, J.-E.; Arnold, F. H. J. Am. Chem. Soc. 2006, 128, 6058e6059.
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C(sp2)eO up to 9:1; (c) Vanover, E.; Huang, Y.; Xu, L.; Newcomb, M.; Zhang, R.
Org. Lett. 2010, 12, 2246e2249 C(sp3)eO/C(sp2)eO up to 5.9:1. For Mn-salen-
catalyzed benzylic hydroxylation reactions, see: (d) Larrow, J. F.; Jacobsen, E.
N. J. Am. Chem. Soc. 1994, 116, 12129e12130; (e) Hamachi, K.; Irie, R.; Katsuki, T.
Tetrahedron Lett. 1996, 37, 4979e4982 For other catalysts catalyzed benzylic
hydroxylation reactions, see: (f) Nagataki, T.; Tachi, Y.; Itoh, S. J. Mol. Catal. A:
Chem. 2005, 225, 103e109 C(sp3)eO/C(sp2)eO up to 8.8:1; (g) Chen, G. S.;
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C(sp2)eO up to 8:1; (h) Matsumoto, T.; Ohkubo, K.; Honda, K.; Yazawa, A.;
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9258e9267 For benzylic oxidation to peroxyethers, see: (i) Rothenberg, G.;
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A solution of copper(II) trifluoromethanesulfonate (3.7 mg,
0.01 mmol) and ligand 10a (2.8 mg, 0.012 mmol) in dry acetone
(2 mL) was stirred at room temperature for 1 h. n-Hexadecane was
added as internal standard. Phenylhydrazine (1.3 mg, 0.012 mmol)
was added to this dark brown solution, and the solution became
purple immediately. After stirring for additional 5 min, tetralin
(132 mg, 1 mmol) was added through a syringe, and the oxidant
tert-butyl benzoate (39 mg, 0.2 mmol) was added afterwards. The
mixture was then stirred at 30 ꢀC for a certain time until the re-
action was completed (determined by the disappearance of the
perester by TLC). After the mixture was filtered with diethyl ether
through a short pipette plug of silica, a sample was taken for
analysis. Yields of the products were determined by gas chroma-
tography with response factors using the n-hexadecane internal
standard. Verification of the products was done by comparison with
authentic samples.
kova, A. M.; Crabtree, R. H. J. Mol. Catal. A: Chem. 2009, 312, 1e6 C(sp3)eO/
2
ꢀ
C(sp )eO up to 4.8:1; (m) Novak, P.; Correa, A.; Gallardo-Donaire, J.; Martin, R.
Angew. Chem., Int. Ed. 2011, 50, 12236e12239; (n) Huang, J.; Li, L. T.; Li, H. Y.;
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references therein.
The GC conditions for the determination of the yield for each
product are: HP-5 column, 30 mꢁ0.32 mmꢁ0.25
mm; N2, 1.0 mL/
min; started from 60 ꢀC and programmed at 5 ꢀC/min to 250 ꢀC.
tR¼12.7 min (substrate1a, tetralin), tR¼17.5 min (product, 3a,1,2,3,4-
tetrahydronaphthalen-1-ol), tR¼18.1 min (product 5a, 1-tetralone),
tR¼23.1 min (internal standard, n-hexadecane), tR¼33.4 min
(product 4a, 1,2,3,4-tetrahydronaphthalen-1-yl benzoate). Analytic
data of products are listed in the Supplementary data.
7. For
a
review on copper-catalyzed allylic oxidation reaction (Khar-
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We thank the National Natural Science Foundation of China and
the National Basic Research Program of China (2011CB808600), and
the ‘111’ project (B06005) of the Ministry of Education of China for
financial support.