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ChemComm
Page 4 of 4
DOI: 10.1039/C8CC03722A
COMMUNICATION
Journal Name
A: Control experiments
Chemistry
,
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1.0 equiv Cat.1
Ar2
Cat.1: (NH4)5[IMo6O18(OH)6]
OH
O
(a)
NaCl (0.1 equiv)
H2O/CH3CN =1/1 (2 ml)
70 oC, 12h
96 % yield
0.1 equiv Cat.
O2(1.0 atm)
OH
O
Cat.
yield
(b)
-
-
NaCl (0.1 equiv)
H2O/CH3CN =1/1 (2 ml)
70 oC, 24h
<5
H5IO6
<5
(NH4)6Mo7O24
H5IO6
+
32
(NH4)6Mo7O24
Fig. 2 Experimental studies providing insight into the mechanism
of the iodine-catalyzed oxidation of alcohols.
2
3
Iodine-POMs-mediated oxidation of the alcohols and dioxygen-
coupled oxidation of [IVMoVI6O24]7-. For the inorganic-ligand
supported iodine catalysts, the two oxidizing equivalents required
for oxidation are stored at the iodine center. The addition of
additives can significantly influence the reaction; this is most likely
due to the Cl− or Ac− acting as an electron-transfer mediator to
improve the electron transfer efficiency of the iodine-POMs catalyst
system. This mechanism has important implications for the
development of new catalytic oxidation reactions.
4
5
6
7
8
R. Mu, Z. Liu, Z. Yang, Z. Liu, L. Wu and Z.-L. Liu, Adv. Synth.
Catal., 2005, 347, 1333-13336.
Fig. 3 Proposed mechanism for the iodine-POM-catalyzed oxidation
of alcohols
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In summary, we have developed a highly efficient and mild
inorganic-ligand coordinated iodine-POM-catalyzed oxidation
system for a variety of alcohols. The catalyst system exhibits a wide
substrate tolerance with excellent selectivity and recoverability.
This catalytic system takes safety into account and avoids using any
organic ligand and toxic oxidants, which is beneficial for its use in
pharmaceuticals, fragrances, and food additives. The generality of
this methodology gives it the potential to be used on an industrial
scale.
9
This work was supported by the National Natural Science
Foundation of China (Nos. 21471087, 21631007, 21225103,
21221062), Doctoral Fund of Ministry of Education of China No.
20130002110042, Tsinghua University Initiative Foundation
Research Program No. 20131089204 and the State Key Laboratory
of Natural and Biomimetic Drugs K20160202. The start-up fund of
Shanghai Institute of Technology is also gratefully acknowledged.
10 S.-S. Wang and G.-Y. Yang, Chem. Rev., 2015, 115, 4893–4962.
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Am. Chem. Soc., 1948, 70, 1291-1292. (c) B. Hasenknopf, R.
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and Y.-G. Wei, Chem. Eur. J., 2011, 17, 12002-12005.
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Notes and references
1
Selected reviews and books: (a) A. Varvoglis, The Organic
Chemistry of Polycoordinated Iodine, Wiley, New York, 1992.
(b) P. J. Stang and V. V. Zhdankin, Chem. Rev. 1996, 96, 1123-
1178. (c) K. Y. Akiba, Chemistry of Hypervalent Compounds,
John Wiley & Sons, New York, 1999. (d) V. V. Zhdankin and P.
J. Stang, Chem. Rev. 2002, 102, 2523-2584. (e) T. Wirth,
Oxidations and rearrangements. In Hypervalent Iodine
13 A. M. Khenkin and R. Neumann, Adv. Synth. Catal., 2002, 9, 344-
352.
4 | J. Name., 2012, 00, 1-3
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