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Organic & Biomolecular Chemistry
Page 4 of 5
COMMUNICATION
Journal Name
‡ A typical procedure: Under an oxygen atmosphere (1 atm), 1a
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(0.2 mmol), NH4OAc (0.8 mmol), metallic Cu (0.02 mol) and
dioxane (1.0 mL) were placed into a glass tube (25 mL) and
o
sealed. The mixture was heated at 130 C for 24 hours. After
removal of the volatiles in vacuum, the residues were purified by
chromatography on silica gel (particle size 37-54 μm) using ethyl
acetate/petroleum ether as eluent to obtain 85% yield of 2a.
1
2
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reaction conditions, giving 2s in 65% yield. However, in the
absence of CuI, the yield of 2s was 0% and imine 5b was
formed instead. In the presence of water, imine 5b could be
converted to 2s even without CuI. These results indicate that
water and copper catalyst would promote the amidation via
path a.
3
4
N
CHO
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2
PhNH
2
equiv
2s
(a)
1 mL dioxane, O2 130 o 24 h
,
C,
10 mol% CuI, 65%
3a
Ph
was
without CuI,
5b
formed
0%,
N
N
2
PhNH
10
H
2O
,
equiv
equiv
2
2s
(b)
1 mL dioxane, O2 130 o 24 h
,
C,
10 mol% CuI, 81%
without CuI, 39%
5b
5
12 (a) J. Liu, X. Zhang, H. Yi, C. Liu, H. Zhang, K. Zhuo and A. Lei,
Angew. Chem. Int. Ed., 2015, 54, 1261; (b) J. D. Houwer, K. A.
Tehrani and B. U. W. Maes, Angew. Chem. Int. Ed., 2012, 51,
2745.
13 In the absence of NH4OAc, 3a could be confirmed by GC-MS
when 2-methylquinoline was treated under the standard
reaction conditions.
14 The aerobic oxidation of methyl groups was thought to be
rate determining. When the reaction of 2-methylquinoline
with NH4OAc was conducted at 100 oC, no product could be
detected, whereas quinoline-2-carbaldehyde 3a gave 2a in
29% yield under similar reaction conditions.
15 Considering that the reaction did not take place with toluene,
3-methylquinoline and 2-methylthiophene, the nitrogen
atom in 1 would be crucial and the methyl group should be
located at 2- or 4-position. Besides, suitable pH condition
was required. Thus on the basis of these results and reported
literatures, a plausible mechanism for the copper catalysed
aerobic oxidation of azaarylmethanes was proposed below.
6
7
+
-
H
N
suitable
pH
N
H
N
[Cun]
O2
8
9
(a) M. H. S. A. Hamid, C. L. Allen, G. W. Lamb, A. C. Maxwell,
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David and D. Milstein, Science, 2007, 317, 790.
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M. Yuguchi, S. Yamashita and M. Tokuda, J. Am. Chem. Soc.,
2004, 126, 14342; (b) K. Yamaguchi, M. Matsushita and N.
Mizuno, Angew. Chem. Int. Ed., 2004, 43, 1576; (c) S.-I.
Murahashi, T. Naota and E. Saito, J. Am. Chem. Soc., 1986,
108, 7846; (d) J. W. Kim, K. Yamaguchi and N. Mizuno,
O
-[Cun](OH)
N
N
N
O.
[Cun]
[Cun+1
]
O
O
O
For related contributions, see: (a) B. Qian, S. Guo, J. Shao, Q.
Zhu, L. Yang, C. Xia and H. Huang, J. Am. Chem. Soc., 2010,
132, 3650; (b) Z.-J. Cai, S.-Y. Wang and S.-J. Ji, Org. Lett., 2012,
4 | J. Name., 2012, 00, 1-3
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