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ChemComm
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DOI: 10.1039/C7CC02166F
COMMUNICATION
Journal Name
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Y. Jing, C. G. Daniliuc, A. Studer, Org. Lett. 2014, 16, 4932-
4935.
J. Barluenga, M. Marco-Arias, F. González-Bobes, A.
Ballesteros, J. M. González, Chem. Commun. 2004, 2616-
2617.
K. Moriyama, Y. Nakamura, and H. Togo, Org. Lett. 2014, 16,
3812-3815.
a) K. Moriyama, Y. Izumisawa, and H. Togo, J. Org. Chem.
2011, 76, 7249-7255; b) K. Moriyama, M. Takemura, and H.
Togo, Org. Lett. 2012, 14, 2414-2417; c) K. Moriyama, K.
Ishida, and H. Togo, Chem. Commun. 2012, 48, 8574-8576; d)
K. Moriyama, M. Takemura, and H. Togo, J. Org. Chem. 2014
79, 6094-6104; e) K. Moriyama, T. Sugiue, C. Nishinohara, H.
Togo, J. Org. Chem. 2015, 80, 9132-9140; f) K. Moriyama, C.
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85872-85878.
by addition of H2O immediately. By contrast, ganaration of
another
α-radical (path b) is provided alcohols (15) via
formation of A’ and B’ intermediates by above reaction
mechanism. However, 15 is oxidized by aerobic oxidation with
a catalytic amount of bromide to obtain corresponding
7
8
ketones (14) (Scheme S1, Eq. S2). The
oxidation of bromide provides -bromo ketones (
bromination, it is important to add p-NO2C6H4SO2NH2 catalyst
to promote the -bromination of 14 by activation of a bromo
source. In the reaction of cyclic ethers ), second
bromination of followed by intramolecular cyclization gives
α
-bromination of 14 via
α
2). In the
α-
α
(
3
a
,
2
4
after the formation of
mechanism.
2 through the above reaction
In conclusion, we developed a catalytic DDF of ethers via
9
a) G. Arabaci, X.-C. Guo, K. D. Beebe, K. M. Coggeshall, D.
dealkylation–oxidation–α
oxidation of bromide to obtain the corresponding
-bromination
by
the
aerobic
-bromo
Pei, J. Am. Chem. Soc. 1999, 121, 5085-5086; b) G. Arabaci, T.
Yi, H. Fu, M. E. Porter, K. D. Beebe, D. Pei, Bioorg. Med.
Chem. Lett. 2002, 12, 3047-3050; c) S. Conde, D. L. Pérez, A.
Martínez, C. Perez, F. J. Moreno, J. Med. Chem. 2003, 46,
4631-4633.
α
ketones and 3,3-dibromo tetrahydrofuran-2-ols in high yields.
This DDF is expected to further expand fine organic reactions.
The development of this catalytic system in aerobic
transformation and the application of this oxygen-containing
heterocycles are underway in our laboratory.
10 a) N. De Kimpe, R. Verhé The Chemistry of
α
α-Haloketones, α-
Heteroaldehydes, and -Haloimines, Wiley, Nuw York, 1999;
b) A. W. Erian, S. M. Sherif, H. M. Gaber, Molecules 2003, 8,
793-865.
11 a) R. Mu, Z. Liu, Z. Yang, Z. Liu, L. Wu, Z.-L. Liu, Adv. Synth.
Catal. 2005, 347, 1333-1336; b) M. Uyanik, R. Fukatsu, K.
Ishihara, Chem. Asian J. 2010, 5, 456-460.
Notes and references
12 Treatment of p-NO2C6H4SO2NH2 with aq. HBr and NaNO2 in
MeCN under O2 at 60 oC for 24 h did not provide p-
NO2C6H4SO2NBr2.
13 W. Z. Yu, F. Chen, Y. A. Cheng, Y.-Y. Yeung, J. Org. Chem.
2015, 80, 2815-2821.
14 This reaction of 1a under the optimized conditions (Scheme
1
For reviews on multi functionalization, see: a) A. Minatti, K.
Muñiz, Chem. Soc. Rev. 2007, 36, 1142-1152; b) E. M.
Beccalli, G. Broggini, M. Martinelli, S. Sottocomola, Chem.
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Y. Shimizu, M. Kanai, Tetrahedron Lett. 2014, 55, 3727-3737;
f) D. Qiu, J. Shi, Y. Li, Synlett 2015, 26, 2194-2198.
1) provided benzaldehyde (38% yield) and benzoic acid (37%)
as byproduct together with 2a
15 F. Minisci, O. Porta, F. Recupero, C. Punta, C. Gambarotti, M.
.
2
Selected recent report for the reductive dual
Pierini, L. Galimberti, Synlett, 2004, 2203-2205.
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,
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,
12, 3590-3593; h) G. Fumagalli, P. T. G. Rabet, S. Boyd, M. F.
Greaney, Angew. Chem. Int. Ed. 2015, 54, 11481-11484; i) R.
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Selected recent report for the retained dual
functionalization: a) T. Morishita, H. Fukushima, H. Yoshida,
J. Ohshita, A. Kumai, J. Org. Chem. 2008, 73, 5452-5457; b) A.
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D. Talwar, A. Gonzalez-de-Castro, H. Y. Li, J. Xiao, Angew.
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4 | J. Name., 2012, 00, 1-3
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