Nickel-catalyzed sonogashira reaction in PEG-400/H O
2
M. R. J. Elsegood, A. J. Fletcher, P. J. Lovell, J. Org. Chem. 2005, 70,
at 100°C in PEG-400/H
responding arylacetylenes in good to excellent yields. Furthermore,
the NiCl (PPh /CuI/PEG-400/H O system could be recycled and
2 2 3
O (3:2) with K CO as base to afford the cor-
1
2
0615; d) K. Hiroya, S. Matsumoto, T. Sakamoto, Org. Lett. 2004, 6,
953; e) K. C. Nicolaou, P. G. Bulger, D. Sarlah, Angew. Chem. Int. Ed.
2
)
3 2
2
2005, 44, 442.
reused six times without significant loss of catalytic activity. Our sys-
tem not only avoids the use of easily volatile organic solvents but
also solves the basic problem of catalyst reuse, and this protocol will
serve as an efficient and green way to prepare a variety of
arylacetylenes. Currently, further efforts to extend the application
of the system to other nickel-catalyzed organic transformations
are underway in our laboratory.
[4] N. D. P. Cosford, L. Tehrani, J. Roppe, E. Schweiger, N. D. Smith,
J. Anderson, L. Bristow, J. Brodkin, X. Jiang, I. McDonald, S. Rao,
M. Washburn, M. A. Varney, J. Med. Chem. 2003, 46, 204.
[
5] a) O. Mongin, L. Porres, L. Moreaux, J. Merta, M. Blanchard-Desce, Org.
Lett. 2002, 4, 719; b) L. Brunsveld, E. W. Meijer, R. B. Prince, J. S. Moore,
J. Am. Chem. Soc. 2001, 123, 7978.
[6] a) N. E. Leadbeater, M. Marco, Chem. Rev. 2002, 102, 3217; b) L. Yin,
J. Liebscher, Chem. Rev. 2007, 107, 133; c) A. Molnar, Chem. Rev.
2011, 111, 2251.
[
7] a) M. Carril, A. Correa, C. Bolm, Angew. Chem. Int. Ed. 2008, 47, 4862; b)
D. N. Sawant, P. J. Tambade, Y. S. Wagh, B. M. Bhanage, Tetrahedron Lett.
2010, 51, 2758.
Experimental
[
8] L. Feng, F. Liu, P. Sun, J. Bao, Synett 2008, 1415.
All chemicals were of reagent grade and used as purchased. All
coupling products were characterized by comparison of their
spectra and physical data with those of authentic samples. Infra-
red spectra were recorded with a PerkinElmer 683 instrument.
[9] a) I. P. Beletskaya, G. V. Latyshev, A. V. Tsvetkov, N. V. Lukashev,
Tetrahedron Lett. 2003, 44, 5011; b) L. Wang, P. Li, Y. Zhang, Chem.
Commun. 2004, 514; c) O. Vachorkin, D. Barmaz, V. Proust, X. Hu,
J. Am. Chem. Soc. 2009, 131, 12078; d) J. Yi, X. Lu, Y.-Y. Sun, B. Xiao,
L. Liu, Angew. Chem. Int. Ed. 2013, 52, 12409.
10] a) K. Okuro, M. Furuune, M. Enna, M. Miura, M. Nomura, J. Org. Chem. 1993,
58, 4716; b) R. K. Gujadhur, C. G. Bates, D. Venkataraman, Org. Lett. 2001, 3,
4315; c) D. Ma, F. Liu, Chem. Commun. 2004, 1934; d) B.-X. Tang, F. Wang,
J.-H. Li, Y.-X. Xie, M.-B. Zhang, J. Org. Chem. 2007, 72, 6294; e) F. Liu, D. Ma,
J. Org. Chem. 2007, 72, 4844; f) F. Monnier, F. Turtaut, L. Duroure,
M. Taillefer, Org. Lett. 2008, 10, 3203; g) S. Inack-Ngi, R. Rahmani,
L. Commeiras, G. Chouraqui, J. Thibonnet, A. Duchene, M. Abarbri,
J.-L. Parrain, Adv. Synth. Catal. 2009, 351, 779; h) E. Zuidema, C. Bolm,
Chem. Eur. J. 2010, 16, 4181; i) J. Santandrea, A.-C. Bedard, S. K. Collins,
Org. Lett. 2014, 16, 3892.
1
H NMR spectra were recorded using a Bruker Avance 400 MHz
[
spectrometer with tetramethylsilane as an internal standard in
1
3
CDCl
Avance 400 MHz spectrometer in CDCl
are uncorrected.
3
as solvent. C NMR spectra were recorded with a Bruker
3
as solvent. Melting points
General procedure for nickel-catalyzed sonogashira coupling
reaction of aryl iodides with alkynes in PEG-400/H
2
O
[
[
11] a) J. D. Revell, A. Ganesan, Org. Lett. 2002, 4, 3071; b) W. Miao,
T. H. Chan, Org. Lett. 2003, 5, 5003; c) C. J. Mathews, P. J. Smith,
T. Welton, Chem. Commun. 2000, 1249; d) M. Cai, Y. Wang, W. Hao,
Green Chem. 2007, 9, 1180; e) H. Zhao, Z. Xi, W. Hao, M. Cai, New J.
Chem. 2011, 35, 2661; f) J. P. Hallett, T. Welton, Chem. Rev. 2011, 111,
A mixture of aryl iodide (0.5 mmol), terminal alkyne (0.6 mmol),
CO (1.0 mmol), NiCl (PPh (0.025 mmol) and CuI (0.05 mmol)
in PEG-400 (3.0 ml) and H O (2.0 ml) was stirred at 100°C under ar-
gon for 2 h. After being cooled to room temperature, the resulting
mixture was extracted with petroleum ether (3 × 10 ml). The residue
of the extraction was subjected to a second run of the Sonogashira
reaction by charging with the same substrate (aryl iodide, terminal
K
2
3
2
3 2
)
2
3508.
12] a) S. Chandrasekhar, C. Narsihmulu, S. S. Sultana, N. R. Reddy, Org.
Lett. 2002, 4, 4399; b) J.-H. Li, W.-J. Liu, Y.-X. Xie, J. Org. Chem.
2
005, 70, 5409; c) L. Liu, Y. Zhang, Y. Wang, J. Org. Chem. 2005,
alkyne and K
2
CO
3
) under the same conditions without further addi-
or CuI. The combined ether phase was concen-
70, 6122; d) W. Han, C. Liu, Z.-L. Jin, Org. Lett. 2007, 9, 4005; e)
L. Wang, Y. Zhang, L. Liu, Y. Wang, J. Org. Chem. 2006, 71, 1284; f)
L. Ackermann, R. Vicente, Org. Lett. 2009, 11, 4922; g) S. Shi,
Y. Zhang, J. Org. Chem. 2007, 72, 5927; h) Q. Zhou, S. Wei, W. Han,
J. Org. Chem. 2014, 79, 1454; i) H. Zhao, M. Cheng, J. Zhang,
M. Cai, Green Chem. 2014, 16, 2515; j) J. Xia, M. Cheng, Q. Chen,
M. Cai, Appl. Organomet. Chem. 2015, 29, 113; k) W.-J. Zhou,
K.-H. Wang, J.-X. Wang, J. Org. Chem. 2009, 74, 5599.
tion of NiCl (PPh
2
3
)
2
trated under reduced pressure. The residue was purified by flash
column chromatography on silica gel using petroleum ether or a
mixture of petroleum ether and EtOAc as eluent.
[18]
[19]
[18]
[19]
[18]
Compounds 3a–3c, 3d and 3e, 3f, 3g, 3h–3l, 3m
[20]
[21]
[18]
[22]
and 3n, 3o–3q, 3r–3t, and 3u and 3v are known com-
1
13
[13] a) N. R. Candeias, L. C. Branco, P. M. P. Gois, C. A. M. Afonso,
A. F. Trindade, Chem. Rev. 2009, 109, 2703; b) D. E. Bergbreiter,
J. Tian, C. Hongfa, Chem. Rev. 2009, 109, 530; c) C. K. Z. Andrade,
L. M. Alves, Curr. Org. Chem. 2005, 9, 195; d) J. Chen, S. K. Spear,
J. G. Huddleston, R. D. Rogers, Green Chem. 2005, 7, 64; e)
V. Declerck, E. Colacino, X. Bantreil, J. Martinez, F. Lamaty, Chem.
Commun. 2012, 48, 11778.
pounds and were characterized by comparing their H NMR,
NMR and infrared spectra with those found in the literature.
C
Acknowledgments
We thank the National Natural Science Foundation of China (no.
1462021) and Key Laboratory of Functional Small Organic Molecule,
[
14] X. Bantreil, M. Sidi-Ykhlef, L. Aringhieri, E. Colacino, J. Martinez,
2
F. Lamaty, J. Catal. 2012, 294, 113.
Ministry of Education (no. KLFS-KF-201213) for financial support.
[
[
15] S. Chandrasekhar, S. J. Prakash, C. L. Rao, J. Org. Chem. 2006, 71, 2196.
16] a) C. S. Cho, N. T. Tran, Catal. Commun. 2009, 11, 191; b) Y. Cao,
Z. Zhang, Y. Guo, G. Wu, Synth. Commun. 2008, 38, 1325.
[
17] a) G. A. Burley, D. L. Davies, G. A. Griffith, M. Lee, K. Singh, J. Org. Chem.
References
2
010, 75, 980; b) E. Colacino, L. Dalch, J. Martinez, F. Lamaty, Synlett
[
1] a) S. Patai (Ed), Chemistry of Triple-Bonded Functional Groups, Wiley,
New York, 1994; b) J. Liu, J. W. Y. Lam, B. Z. Tang, Chem. Rev. 2009,
2007, 1279; c) V. Declerck, J. Martinez, F. Lamaty, Synlett 2006, 3029;
d) S. Chandrasekhar, S. S. Sultana, S. R. Yaragorla, N. R. Reddy,
Synthesis 2006, 839; e) J. She, Z. Jiang, Y. Wang, Tetrahedron Lett.
2009, 50, 593.
109, 5799; c) H. K. Bisoyi, S. Kumar, Chem. Soc. Rev. 2010, 39, 264.
[2] a) K. Sonogashira, in Handbook of Organopalladium Chemistry for
Organic Synthesis (Eds: E.-I. Negishi, A. Meijere), Wiley-VCH, New York,
[18] H. Huang, H. Liu, H. Jiang, K. Chen, J. Org. Chem. 2008, 73, 6037.
2
002, p. 493. b) E.-I. Negishi, L. Anastasia, Chem. Rev. 2003, 103,
[19] B. Liang, M. Dai, J. Chen, Z. Yang, J. Org. Chem. 2005, 70, 391.
[20] K. Park, G. Bae, J. Moon, J. Choe, K. H. Song, S. Lee, J. Org. Chem. 2010,
1979; c) R. Chinchilla, C. Najera, Chem. Rev. 2007, 107, 874; d)
H. Plenio, Angew. Chem. Int. Ed. 2008, 47, 6954; e) R. Chinchilla,
C. Najera, Chem. Soc. Rev. 2011, 40, 5084.
75, 6244.
[21] T. Mino, Y. Shirae, T. Saito, M. Sakamoto, T. Fujita, J. Org. Chem. 2006, 71,
[
3] a) I. Paterson, R. D. M. Davies, R. Marquez, Angew. Chem. Int. Ed.
9499.
2
001, 40, 603; b) C. C. Li, Z. X. Xie, Y. D. Zhang, J. H. Chen, Z. Yang,
[22] G. A. Molander, B. W. Katona, F. Machrouhi, J. Org. Chem. 2002, 67,
J. Org. Chem. 2003, 68, 8500; c) J. M. Pedersen, W. R. Bowman,
8416.
Appl. Organometal. Chem. 2015, 29, 846–849
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