Li et al.
FULL PAPER
Table 3 CuI/L3 catalyzed annulation of imidazole-2-carboxal-
dehyde with substituted 2-haloanilinea
Conclusions
In conclusion, we have established a simple one-pot
copper-catalyzed method allowing the direct synthesis
of various of pyrrolo[1,2-a]- and imidazo[1,2-a]quin-
oxalines from substituted 2-haloanilines with pyrrole-
and imidazole-2-carboxaldehyde in moderate to excel-
lent yields by using 2-hydroxybenzohydrazide as an
idea ligand. The low catalyst loading, stable and easy-
synthesis of ligand, experimental simplicity and without
inert atmosphere are the features of the catalytic process
presented in the current paper.
5 mol% CuI
10 mol% L3
N
X
N
N
N
CHO
R
N
H
R
Cs2CO3, DMF
120 oC, 24 h
NH2
4
2 X = I, Br, Cl
5
R = H, CH3, F, Cl, Br
O
NH2
N
H
OH
L3
Entry
1
2-Haloaniline
Product
Yieldb/%
68
Acknowledgement
5
We thank the National Basic Research Program of
China (973 Program, No. 2012CB722603), the NSFC
(Nos. 21103114, 21463022) and Training Program for
Distinguished Youth Scholars of Shihezi University (No.
2014ZRKXJQ05) for their financial support.
I
N
N
N
5a
NH2
H3C
I
N
H3C
N
2
3
4
5
6
7
8
9
56
63
5b
5c
5d
5e
5f
NH2
References
N
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I
N
N
N
H3C
F
NH2
H3C
F
I
N
N
65
NH2
N
Cl
Br
I
N
Cl
Br
N
68
NH2
N
I
N
N
N
55
NH2
I
N
N
N
N
40
5g
5a
5a
N
NH2
N
Br
N
N
62
NH2
Cl
N
N
N
trace
NH2
a
Reaction conditions: imidazole-2-carboxaldehyde (0.5 mmol),
2-iodoaniline (0.75 mmol), CuI (0.025 mmol), L3 (0.05 mmol),
Cs2CO3 (1.0 mmol), DMF (1 mL), 120 ℃, 24 h. b Isolated yield.
with imidazole-2-carboxaldehyde that occur in moder-
ate to good yields (Entries 1-8). Unfortunately, the
annulation of imidazole-2-carboxaldehyde with 2-chloro-
aniline under these conditions was still a challenge (En-
try 9).
[3] Huang, A.; Liu, F.; Zhan, C.; Liu, Y.; Ma, C. Org. Biomol. Chem.
2011, 9, 7351.
592
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Chin. J. Chem. 2015, 33, 589—593