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Dalton Transactions
DOI: 10.1039/C3DT51196K
Table 1. Sonogashira Coupling of activated and nonꢀactivated
aryl halides with Alkynes RC≡CHa
Notes and references
§ Crystal data for 1a (CCDC 923839): C56H88Cu4Fe2N4P4S4, FW=
35 1435.28, orthorhombic, Aba2, a = 32.8531(4) Å, b = 32.0553(6) Å, c =
21.0880(3) Å, V = 22208.1(6) Å3, T = 150(2) K, Z = 12, ꢀ, mmꢀ1 = 1.742,
dcalc, g cmꢀ3 = 1.288, R1 [I > 2σ(I)] = 0.0466, wR2 = 0.1012, S = 1.093.
Crystal data for 1b (CCDC 920724): C56H88Cu4Fe2N4P4S4, FW= 1435.28,
orthorhombic, Aba2, a = 32.822(3) Å, b = 32.088(2) Å, c = 21.1255(9) Å,
Entry R X Copper
source
Palladium source Alkynylation
Alkyne
dimerization
yield [%]b
0
([Pd(allyl)Cl]2) product yield
[%]b
0
40 V = 22249(3) Å3, T = 293(2) K, Z = 12, ꢀ, mmꢀ1 = 1.739, dcalc, g cmꢀ3
1.285, R1 [I > 2σ(I)] = 0.0755, wR2 = 0.1298, S = 1.119. For 1a & 1b, the
SQUEEZE option in PLATON was used to remove the disordered solvent
molecules.
=
1.
2.
H
H
Br 0.1 mol%
complex 1
Br 0.1 mol%
CuI
0
0
1
(a) K.ꢀS. Gan, T.S.A. Hor, In Ferrocenes: Homogeneous Catalysis,
Organic Synthesis, Materials Science; A. Togni, T. Hayashi, Eds.;
VCH: New York, 1995, p 3; (b) T. Hayashi, In Ferrocenes:
Homogeneous Catalysis, Organic Synthesis, Materials Science; A.
Togni, T., Eds.; VCH: New York, 1995, p 105; (c) A.W. Chien,
T.S.A. Hor, In Ferrocenes: Ligands, Materials and Biomolecules; P.
Štèpnićka, Eds.; John Wiley & Sons, Ltd.: West Sussex, 2008, p 33;
(d) T.J. Colacot, S. Parisel, In Ferrocenes: Ligands, Materials and
Biomolecules; P. Štèpnićka Ed.; John Wiley & Sons, Ltd.: West
Sussex, 2008, p 117; (e) D.J. Young, S.W. Chien, T.S.A. Hor, Dalton
Trans., 2012, 41, 12655.
3.
4.
5.
H
H
H
Br
Br
0.2 mol%
0.2 mol%/dtbpf 10
0
0
no
50
45
50
55
60
Br 0.1 mol% 0.2 mol%
CuI
20
6.
7.
8.
9.
H
H
H
H
Br 0.1 mol% 0.2 mol%/dtbpf 25
CuI
60
Br 0.1 mol% 0.2 mol%
90
95
65
75
99
80
traces
no
complex 1
I
0.1 mol% 0.2 mol%
complex 1
Cl 0.1 mol% 0.2 mol%
30
2
(a) Z. Csok, O. Vechorkin, S.B. Harkins, R. Scopelliti, X. Hu, J. Am.
Chem. Soc. 2008, 130, 8156; (b) S. Jamali, S.M. Nabavizadeh, M.
Rashidi, Inorg. Chem. 2008, 47, 5441; (c) A. SerraꢀMuns, A. Jutand,
M. MorenoꢀManas, R. Pleixats, Organometallics 2008, 27, 2421; (d)
R. Kuwano, H. Kusano, Org. Lett. 2008, 10, 1979; (e) G.D. Vo, J.F.
Hartwig, Angew. Chem., Int. Ed. 2008, 47, 2127; (f) M. Kawatsura,
T. Hirakawa, T. Tanaka, D. Ikeda, S. Hayase, T. Itoh, Tetrahedron
Lett. 2008, 49, 2450; (g) A.P. Shaw, H. Guan, J.R. Norton, J.
Organomet. Chem. 2008, 693, 1382; (h) L.ꢀC. Song, H.ꢀT. Wang, J.ꢀ
H. Ge, S.ꢀZ. Mei, J. Gao, L.ꢀX. Wang, B. Gai, L.ꢀQ. Zhao, J. Yan,
Y.ꢀZ. Wang, Organometallics 2008, 27, 1409; (i) N. Fey, J.N.
Harvey, G.C. LloydꢀJones, P. Murray, A.G. Orpen, R. Osborne, M.
Purdie, Organometallics 2008, 27, 1372; (j) T. Dahl, C.W. Tornoee,
B. BangꢀAndersen, P. Nielsen, M. Joergensen, Angew. Chem., Int.
Ed. 2008, 47, 1726; (k) B.ꢀT. Guan, S.ꢀK. Xiang, B.ꢀQ. Wang, Z.ꢀP.
Sun, Y. Wang, K.ꢀQ. Zhao, Z.ꢀJ. Shi, J. Am. Chem. Soc. 2008, 130,
3268; (l) T. Jensen, H. Pedersen, B. BangꢀAndersen, R. Madsen, M.
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complex 1
10. CH3 Br 0.1 mol% 0.2 mol%
complex 1
11. CH3 I 0.1 mol% 0.2 mol%
complex 1
traces
No
12. CH3 Cl 0.1 mol% 0.2 mol%
complex 1
traces
aAll reactions were carried out using 3.38 X 10ꢀ3 mol activated and nonꢀ
activated aryl halides, phenylacetylene (2 equivalent), K2CO3 (2 equivalent),
0.1 mol% of 1/CuI with 0.2 mol% of [Pd(allyl)Cl]2 and the catalytic system 65
stirred at 120°C over 20 h in 10 mL of DMF under nitrogen.
bIsolated yield.
and 65%, respectively, Table 1 entries 7, 8, and 9) by
employing 0.1 mol% of 1, 0.2 mol% of the palladium source,
and the nonꢀactivated iodo, bromo or chlorobenzene. Under
the same catalytic conditions the electronꢀrich 4ꢀ
bromotoluene, 4ꢀiodotoluene and 4ꢀchlorotoluene were
70
5
3
4
K.M.Clapham, A.S. Batsanov, R.D.R. Greenwood, M.R. Bryce, A.E.
Smith, B. Tarbit, J. Org. Chem. 2008, 73, 2176.
L.E. Hagopian, A.N. Campbell, J.A. Golen, A.L. Rheingold, C.
Nataro, J. Organomet. Chem. 2006, 691, 4890.
efficiently coupled resulting in yields of over 75ꢀ99% (75%,
99% and 80%, respectively, Table 1 entries 10, 11, and 12).
75
10 The stability of complex 1 during the course of tandem
catalytic reaction was checked by 31P and 1H NMR
experiments. Upon mixing the complex 1 with 0.5 equivalent
of the [Pd(allyl)Cl]2 and heating for 2 h at 120°C, a portion of
the dtbpf ligand is transferred to palladium, giving rise to the
15 palladium complex [PdCl(ꢀ1ꢀC3H5)(κ2ꢀP,Pꢀdtbpf)], clearly
characterized in the 31P NMR by two signals at 64.38 ppm
(complex 1) and 57.27 ppm (palladium complex) of almost
equal intensity (See Fꢀ11 & Fꢀ12 supporting material). Upon
heating the mixture for 20 h at 120°C, the total transfer of the
20 ligand from copper to palladium centre has been observed
(See Fꢀ13 supporting material).
In conclusion, we have synthesized and characterized the
cubane tetranuclear Cu(I) complex [Cu4(ꢀ3ꢀSCN)4(κ1ꢀP,Pꢀ
dtbpf)2] in the solid state and in solution. The 31P NMR study
25 shows that complex 1 is unstable during the course of tandem
catalytic reaction and dtbpf ligand migrates to palladium(II)
from copper(I) which promotes palladium Sonogashira crossꢀ
coupling of activated and nonꢀactivated aryl halides.
5
6
7
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80
8
9
85 10 (a) L. Wu, J.F. Hartwig, J. Am. Chem. Soc. 2005, 127, 15824; (b) T.
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90
N.J. Taylor, J. Am. Chem. Soc. 2003, 125, 12700; (g) P.W.N.M. van
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95
100
We thank the Department of Science and Technology,
30 New Delhi (SR/FT/CSꢀ104/2011) for financial support. The
authors sincerely thank the reviewers for their valuable
suggestions and Prof. A.L. Spek, for help in crystallography.
14 M. Beaupérin, A Job, H Cattey, S. Royer, P. Meunier, J.ꢀC. Hierso,
Organometallics 2010, 29, 2815.
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