T. Ponpandian, S. Muthusubramanian / Tetrahedron Letters 53 (2012) 4248–4252
4251
O
OH
CuBr (5 mol%)
L-proline (15 mol%)
I
+
OH
+
K2CO3 (2 equ)
DMF, 100 oC,15 h
O
O
O
O
O
8
9
Scheme 3. Reaction between 2-iodobenzoic acid and phenylpropiolic acid.
3. (a) Castro, C. E.; Gaughan, E. J.; Owsley, D. C. J. Org. Chem. 1966, 31, 4071; (b)
Taylor, E. C.; Katz, A. H.; Salgado Zamora, H. Tetrahedron Lett. 1985, 26, 5963; (c)
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W.; Yum, E. K. Tetrahedron Lett. 2004, 45, 693; (f) Hiroya, K.; Itoh, S.; Sakamoto,
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Y.; Kojima, S.; Sakamoto, T. Heterocycles 1986, 43, 2741; (c) Kondo, Y.; Kojima,
S.; Sakamoto, T. J. Org. Chem. 1997, 62, 6507; (d) Rodrigues, L.; Koradin, C.;
Dohle, W.; Knochel, P. Angew. Chem., Int. Ed. 2000, 39, 2488; (e) Sanz, R.;
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trifluoromethyl anion (as fluoroform) has been noticed, which is a
very rare phenomenon.16 The structure of indolo[1,2-c]quinazo-
lin-6(5H)-one 7 was confirmed by spectral data (ESI-MS, 1H NMR,
13C NMR and FT IR) and also matched with the previously
reported.17 Recently, Ma’s group18 have synthesised the 2-trifluo-
romethylindole and 2-trifluoromethylbenzimidazole derivatives
from 2-iodotrifluoroacetanilide with ethyl acetoacetate and pri-
mary amine respectively using CuI/L-proline catalytic system,
where no case of trifluoromethyl anion elimination has been
reported.
When the reaction between 2-iodobenzoic acid and phenylpro-
piolic acid was effected under same condition, either 8 or 9 were
not obtained. But when DMF was used as the solvent instead of
DMSO, a mixture of isocoumarin 8 and phthalide 9 was obtained
in equal amount with an overall yield of 52% (Scheme 3).
In summary, we have developed the methodology for the syn-
thesis of 2-aryl indoles related skeleton starting from propiolic acid
and aryl iodides. This conversion tolerates a wide range of func-
tional groups which can be useful for further synthetic transforma-
tion. Additionally, the synthesis of 6H-isoindolo[2,1-a]indol-6-one
and [1,2-c]quinazolin-6(5H)-one has been achieved under the
same condition. The described protocol is more convenient for
the preparation of the target compounds in comparison with the
literature methods2–7 and good to excellent yields can be achieved
using readily available starting materials.
6. Liu, F.; Ma, D. J. Org. Chem. 2007, 72, 4844.
7. Wang, R.; Mo, S.; Lu, Y.; Shen, Z. Adv. Synth. Catal. 2011, 353, 713.
8. (a) Feng, C.; Loh, T. P. Chem. Commun. 2010, 46, 4779; (b) Park, J.; Park, E.; Kim,
A.; Park, S. A.; Lee, Y.; Chi, K. W.; Jung, Y. H.; Kim, I. S. J. Org. Chem. 2011, 76,
2214; (c) Moon, J.; Jang, M.; Lee, S. J. Org. Chem. 2009, 74, 1403; (d) Pan, D.;
Zhang, C.; Ding, S.; Jiao, N. Eur. J. Org. Chem. 2011, 2011, 4751; (e) Yeung, P. Y.;
Chung, K. H.; Kwong, F. Y. Org. Lett. 2011, 13, 2912; (f) Zhao, D.; Gao, C.; Su, X.;
He, Y.; You, J.; Xue, Y. Chem. Commun. 2010, 46, 9049; (g) Moon, J.; Jeong, M.;
Nam, H.; Ju, J.; Moon, J. H.; Jung, H. M.; Lee, S. Org. Lett. 2008, 10, 945; (h)
Bilodeau, F.; Brochu, M. C.; Guimond, N.; Thesen, K. H.; Forgione, P. J. Org. Chem.
2010, 75, 1550; (i) Yu, M.; Pan, D.; Jia, W.; Chen, W.; Jiao, N. Tetrahedron Lett.
2010, 51, 1287; (j) Luo, J.; Lu, Y.; Liu, S.; Liu, J.; Deng, G. J. Adv. Synth. Catal. 2011,
353, 2604; (k) Goossen, L. J.; Rodriguz, N.; Gooban, K. Angew. Chem., Int. Ed.
2008, 47, 3100; (l) Kim, H.; Lee, P. H. Adv. Synth. Catal. 2009, 351, 2827; (m) Li,
M.; Wang, C.; Ge, H. Org. Lett. 2011, 13, 2062.
Acknowledgments
The authors thank DST, New Delhi for assistance under the IRH-
PA program for the NMR facility at Madurai Kamaraj University,
Orchid Chemicals and Pharmaceuticals Ltd for providing facilities
and Dr. Sridharan Rajagopal of Orchid research laboratory for his
support.
9. Trost, B. M. Acc. Chem. Res. 2002, 35, 695.
10. Kolarovic, A.; Faberova, Z. J. Org. Chem. 2009, 74, 7199.
11. (a) Cai, Q.; Zou, B.; Ma, D. Angew. Chem., Int. Ed. 2006, 45, 1276; (b) Ma, D.; Cai,
Q. Acc. Chem. Res. 2008, 41, 1450.
12. (a) Newman, M. S.; Merrill, S. H. J. Am. Chem. Soc. 1955, 77, 5549; (b) Gooben, L.
J.; Rodriguez, N.; Manjolinho, F.; Lange, P. P. Adv. Synth. Catal. 2010, 352, 2913;
(c) Dingyi, Y.; Yugen, Z. Green Chem. 2011, 13, 1275; (d) Zhang, X.; Zhang, W. Z.;
Ren, X.; Zhang, L. L.; Lu, X. B. Org. Lett. 2011, 13, 2402; (e) Park, K.; Palani, T.;
Pyo, A.; Lee, S. Tetrahedron Lett. 2012, 53, 733; (f) Dalcanale, E.; Montanari, F. J.
Org. Chem. 1986, 51, 567; (g) Webb, K. S.; Ruszkay, S. J. Tetrahedron 1998, 54,
401; (h) Hapke, M.; Kral, K.; Spannenberg, A. Synthesis 2011, 642; (i) Chimichi,
S.; Sio, F. D.; Donati, D.; Pepino, R.; Rabatti, L.; Sarti-Fantoni, P. J. Heterocycl.
Chem. 1983, 20, 105.
13. General procedure for the synthesis of 3, 4, 5, 7, 8 and 9. To a mixture of
Pd(PPh3)2Cl2 (2 mol %), CuI (4 mol %) and DMF (15 mL) taken in a flask, aryl
iodide (10 mmol), propiolic acid (12 mmol) and diisopropylamine (25 mmol)
were added in that sequence under nitrogen atmosphere. After stirring the
reaction mixture at room temperature for 5 h, the resulting mixture was
diluted with ethyl acetate, filtered through celite bed, the filtrate was washed
with cold aqueous KOH solution (1 ꢂ 100 mL) and acidified with dilute sulfuric
acid (10% solution) at 0 °C. The solid obtained was extracted with
dichloromethane and the extract was washed with water, brine solution and
dried over anhydrous sodium sulfate. The organic layer was concentrated in
vacuo at 40 °C, dried to get the arylpropiolic acid. Arylpropiolic acid (5 mmol)
or 2-butynoic acid (5 mmol) was transferred into a 30 mL glass tube and then
Supplementary data
Supplementary data associated with this article can be found, in
References and notes
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iodo compound (5 mmol), L-proline (15 mol %), cuprous bromide (5 mol %) and
potassium carbonate (10 mmol) in DMSO or DMF (10 mL) were added in that
order. The sealed tube was then subjected to a vacuum and refilled with
nitrogen for five times under stirring at room temperature. The tube was
placed in an oil bath and heated with stirring at 100 °C for 3–5 h. After the
reaction, the reaction mixture was mixed with ethyl acetate and washed with
water, brine solution and dried over anhydrous sodium sulfate. Removal of the