3
1
2
3
4
O
69
29. Rao, G. K.; Kumar, A.; Ahmed, J.; Singh, A. K. Chem.
Commun. 2010, 46, 5954−5956.
7
0
I
5
, 100°C
71
72
30. Yuan, D.; Huynh, H. V. Organometallics 2010, 29, 6020–6027.
31. Fliedel, C.; Braunstein, P. Organometallics 2010, 29, 5614–
5626.
+
CO
+
Et N, toluene
3
7
7
7
7
7
7
7
3
4
5
6
7
8
9
32. Kostas, I. D.; Steele, B. R.; Terzis, A.; Amosova, S. V.;
Martynov, A. V.; Makhaeva, N. A. Eur. J. Inorg. Chem. 2006,
2642−2646.
Scheme 2. Carbonylative Sonogashira coupling reaction.
5
6
7
8
9
In conclusion, palladium chalcogenolate complexes have
been used as a catalyst in C−C cross-coupling, Suzuki coupling
reactions and carbonylative Suzuki coupling reactions.
Furthermore the catalytic system was also tested for other
carbonylation reaction including carbonylative Sonogashira
33. Rao, G. K.; Kumar, A.; Kumar, B.; Kumar, D.; Singh, A. K.
Dalton Trans. 2012, 41, 1931−1937.
34. Sharma, K. N.; Joshi, H.; Singh, V. V.; Singh, P.; Singh, A. K.
Dalton Trans. 2013, 42, 3908−3918.
80
81
35. Chakraborty, T.; Srivastava, K.; Singh, H. B.; Butcher, R. J. J.
Organomet. Chem. 2011, 696, 2559−2564.
8
8
8
8
8
8
8
8
9
9
9
2
3
4
5
6
7
8
9
0
1
2
1
1
1
0 coupling reaction and aminocarbonylation reaction. The
1 catalytic activity is influenced by the nuclearity of complexes
2 and follow a trend mononuclear > binuclear > trinuclear.
36. Zim, D.; Gruber, A. S.; Ebeling, G.; Dupont, J.; Monteiro, A. L.
Org. Lett. 2000, 18, 2881−2884.
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1
3 Acknowledgments
38. Ohff, M.; Ohff, A.; van der Boom, M. E.; Milstein, D. J. Am.
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1
1
4
The author (DP) is thankful to Department of Atomic Energy
5 for the award of a senior research fellowship (SRF).
39. Beletskaya, I. P.; Ananikov, V. P. Eur. J. Org. Chem. 2007,
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1
6 References and notes
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0
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9
0
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0
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0
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0
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7
8
1. Negishi, E. Handbook of organopalladium chemistry for organic
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1
1
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1
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1
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1
44. Experimental procedure for Suzuki reaction: A two-necked flask
was charged with dioxane (3 mL), aryl halide (1.0 mmol),
2 3
arylboronic acid (1.3 mmol), aqueous K CO (2.0 mmol, 1 mL)
and catalyst (0.1 mol%). The reactants were heated at 100 °C
with stirring for a specified time under a nitrogen atmosphere.
After cooling the reaction mixture to room temperature, the
contents were diluted with water (5 mL), neutralized with dil.
HCl and extracted with hexane (3 × 20 mL). The whole organic
extract was washed with water (2 × 15 mL), dried over
7. Khedkar, M. V.; Tambade, P. J.; Qureshi, Z. S.; Bhanage, B. M.
Eur. J. Org. Chem. 2010, 6981−6986.
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10. Dufour, J.; Neuville, L.; Zhu, J. Chem. Eur. J. 2010, 16,
10523−10534.
11. Lebrun, S.; Couture, A.; Deniau, E.; Grandclaudon, P. Synthesis
2012, 44, 1410−1416.
anhydrous Na
reduced pressure. The residue was characterized by H NMR and
2 4
SO , filtered and the solvent was removed under
1
1
3
1
C{ H} NMR spectra. In case of poor yield of the product or its
contamination with other impurities, the product was
chromatographed on a silica gel column.
12. Wu, W.; Huang, L.; Xiao, L.; Huang, Q.; Tang, R.; Ye, C.; Qin,
J.; Li, Z. RSC Adv. 2012, 2, 6520−6527.
45. Experimental procedure for C−C cross coupling reaction
between an arylhalide and organobismuth compound: To a
dioxane (3 mL) solution of 2-bromobenzaldehyde (170 mg, 0.92
13. Dutta, P.; Yang, W.; Eom, S. H.; Lee, S. -H. Organic
Electronics: Physics, Materials, Applications 2012, 13,
273−282.
mmol) and tol
3
Bi (133 mg, 0.28 mmol) was added powdered
CH NMe )(PPh )]
14. Miyaura, N.; Yanagi, T.; Suzuki, A. Synth. Commun. 1981, 11,
513−519.
K
2
CO (152 mg, 1.10 mmol) and [PdCl(SeCH
3
2
2
2
3
(1.2 mg, 0.002 mmol). The whole was heated at 100 ºC in an oil
bath with stirring for 20 h. The contents were cooled to room
temperature and acidified with dilute HCl (10 mL) and extracted
with ethylacetate (3 × 15 mL). The combined extracts were
washed with water (2 × 15 mL) and brine (15 mL) and dried
15. Ishiyama, T.; Kizaki, H.; Miyaura, N.; Suzuki, A. Tetrahedron
Lett. 1993, 34, 7595–7598.
16. Littke, A. F.; Fu, G. C. Angew. Chem. Int. Ed. 1998, 37,
3387−3388.
17. Wolfe, J. P.; Singer, R. A.; Yang, B. H.; Buchwald, S. L. J. Am.
Chem. Soc. 1999, 121, 9550−9561.
2 4
over anhydrous Na SO . This was filtered and dried under
vacuum to give a yellow oil (148 mg) which was characterized
as 2-tolylbenzaldehyde (42%) and 4,4’-dimethylbiphenyl (28%).
Similarly, other C−C coupling reactions were carried out and
18. Stambuli, J. P.; Kuwano, R.; Hartwig, J. F. Angew. Chem. Int.
Ed. 2002, 41, 4746−4748.
19. Mathews, C. J.; Smith, P. J.; Welton, T. J. Mol. Catal. A: Chem.
2003, 206, 77−82.
3
yields were calculated based on aryl groups of Ar Bi consumed
in the reactions.
20. Kim, J. -H.; Kim, J. -W.; Shokouhimehr, M.; Lee, Y. -S. J. Org.
Chem. 2005, 70, 6714−6720.
46. Rao, M. L. N.; Jadhav, D. N.; Venkatesh, V. Eur. J. Org. Chem.
2009, 4300−4306.
21. John, A.; Ghosh, P. Dalton Trans. 2010, 39, 7183−7206.
22. Li, F.; Bai, S.; Hor, T. S. A. Organometallics 2008, 27, 672–677.
23. Alacid, E.; Najera, C. J. J. Organomet. Chem. 2009, 694,
1658−1665.
47. (a) Barton, D. H. R.; Ozbalik, N.; Ramesh, M. Tetrahedron
1988, 44, 5661−5668; (b) Chaudhari, K. R; Wadawale, A.; Jain,
V. K. J. Organomet. Chem. 2012, 698, 15–21.
48. Experimental procedure for carbonylative Suzuki reaction: To a
100 mL autoclave were added iodobenzene (1.0 mmol), phenyl
24. Corma, A.; Garcia, H.; Leyva, A. Tetrahedron 2004, 60,
8553−8560.
2 2 2 3
boronic acid (1.2 mmol), [PdCl(SeCH CH NMe )(PPh )] (1
25. Mu, B.; Li, T.; Xu, W.; Zeng, G.; Liu, P.; Wu, Y. Tetrahedron
2007, 63, 11475−11488.
mol%), toluene (10 mL) and K CO (3.0 mmol). The mixture
2
3
was first stirred for 10 min. and then flushed with 1 atm CO;
then 200 psi of CO was taken, and the reaction mixture was
heated at 100 °C for 8 h. After completion of the reaction, the
reactor was cooled to room temperature and the remaining CO
gas was carefully vented and the reactor was opened. The reactor
vessel was thoroughly washed with ethyl acetate (2 x 10 mL) to
remove any traces of product and catalyst if present. The catalyst
26. Wang, H.; Zhong, R.; Guo, X. -Q.; Feng, X. -Y.; Hou, X. -F.
Eur. J. Inorg. Chem. 2010, 174−178.
140
141
142
143
144
145
27. Zim, D.; Gruber, A. S.; Ebeling, G.; Dupont, J.; Monteiro, A. L.
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28. Yao, Q.; Kinney, E. P.; Zheng, C. Org. Lett. 2004, 6,
2997−2999.