D. Sémeril, D. Matt et al.
FULL PAPER
oxyphenyl)imidazolium bromide (7),[32] 1-benzyl-3-(2,6-dimeth-
oxyphenyl)imidazolium bromide (8),[32] 5-N-(3-benzyl-1-imid-
azolylium)-4(24),6(10),12(16),18(22)-tetramethylenedioxy-
2,8,14,20-tetra-phenyl-resorcin[4]arene bromide (9)[32] and [Ni-
(cod)2][35] were prepared according to literature procedures.
Crystallographic data for this structure have been deposited with
the Cambridge Crystallographic Data Centre under deposition
number CCDC-814000. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via
www.ccdc.cam. ac.uk/data_request/cif.
Single crystals of 2·iPr2O·1.25CH2Cl2 suitable for diffraction study
were obtained by slow diffusion of diisopropyl ether into a dichlo-
romethane solution of the imidazolium salt. Mr = 2428.85, triclinic,
N-Imidazolyl-4(24),6(10),12(16),18(22)-tetramethylenedioxy-
2,8,14,20-tetrapentyl-resorcin[4]arene (5): A mixture of tetra-
bromocavitand 4 (1.268 g, 1.12 mmol), imidazole (0.091 g,
1.34 mmol), K2CO3 (0.385 g, 2.79 mmol), DMEDA (0.074 g,
0.84 mmol) and CuI (0.160 g, 0.84 mmol) was dissolved in DMF
(20 mL) and the reaction mixture was stirred at 140 °C for one
week. After cooling to room temperature, water (50 mL) and
CHCl3 (50 mL) were added to the mixture. The organic layer was
separated and the aqueous phase was extracted with CHCl3
(2ϫ50 mL). The combined organic layers were washed with aque-
ous 0.2 m Na4EDTA (3ϫ50 mL), the organic layer was dried with
Na2SO4, and the solvent was removed under reduced pressure. The
crude product was purified by flash chromatography (MeOH/
CH2Cl2, 1:99, v/v) to afford a mixture (0.309 g; M1) of di- and
tribrominated mono-imidazolyl-cavitands (Rf in the range 0.64–
0.55 MeOH/CH2Cl2, 4:96, v/v), and a minor mixture (M2) of resor-
cinarenes substituted by two or more imidazolyl groups. n-Butyl-
lithium (1.6 m in hexane, 1.37 mmol) was slowly added to a solution
of M1 (0.309 g) in THF (10 mL) at –78 °C. After 0.5 h, the reaction
was quenched with methanol (0.5 mL) and water (10 mL). The or-
ganic phase was recovered and the aqueous phase was washed with
CH2Cl2 (2ϫ10 mL) and the combined organic phases were dried
with Na2SO4. After filtration, the solution was evaporated to dry-
ness to afford 5 (0.290 g, overall yield 30%). The NMR spectra of
the product were identical to those reported previously for 5.[32]
¯
space group P1, a = 16.0333(7), b = 19.3429(8), c = 24.567(1) Å, α
= 73.138(4), β = 73.940(4), γ = 74.245(4)°, V = 6853.6(5) Å3, Z =
2, Dx = 1.177 mgm–3, λ(Mo-Kα) = 0.71073 Å, μ = 0.749 mm–1,
F(000) = 2578, T = 120(2) K. Data were collected on an Oxford
Diffraction Xcalibur Saphir 3 diffractometer (graphite Mo-Kα radi-
ation, λ = 0.71073 Å). The structure was solved with SIR-97,[36]
which revealed the non-hydrogen atoms of the molecule. After an-
isotropic refinement, many hydrogen atoms were located through
a Fourier difference analysis. The whole structure was refined with
SHELX-97[37] and full-matrix least-square techniques (use of F2; x,
y, z, bij for C, Br, Cl, N and O atoms, x, y, z in riding mode for H
atoms); 1400 variables and 8973 observations with I Ͼ 2.0σ(I);
2
2
calcd. w = 1/[σ2(Fo2) + (0.11P)2] where P = (Fo + 2Fc )/3. R1 =
0.1067, wR2 = 0.3061, Sw = 0.888, Δρ Ͻ 1.898 eÅ–3. The alerts
level A in the cif file are mainly due to the large thermal motions
of the C39···C43 chain, of one of the iPr2O molecules and of the
partial CH2Cl2 molecule. Crystallographic data for this structure
have been deposited with the Cambridge Crystallographic Data
Centre under deposition number CCDC-814023. This data can be
obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam. ac.uk/data_request/cif.
Supporting Information (see footnote on the first page of this arti-
cle): Synthesis and full characterisation of the imidazolium salts
used in this study together with the corresponding 1H and 13C
NMR spectra; general procedure and catalytic results for nickel-
catalysed KTC cross-coupling experiments.
General Procedure for Nickel-Catalysed Kumada–Tamao–Corriu
Cross-Coupling Reactions: A 10 mL-Schlenk tube was filled with a
solution of [Ni(cod)2] in dioxane, a solution of the ligand in diox-
ane, aryl halide (0.5 mmol), PhMgBr (1 m in THF, 1 mL,
1.0 mmol), and decane (0.05 mL, internal reference). Dioxane was
then added so that the total reaction volume was either 1.5 or
0.75 mL, and the reaction mixture was heated for 1 h at 100 °C.
After cooling to room temperature, a small amount (0.5 mL) of the
resulting solution was passed through a Millipore filter and ana-
lyzed by GC. All products were unambiguously identified by NMR
spectroscopic analysis after their isolation. The NMR spectra were
compared to those reported in the literature. Some homocoupling
product (Ph-Ph) was detected in each run, but the Ph-Ph/Ar-Ph
ratio never exceeded 15% (see the Supporting Information).
Acknowledgments
The authors thank the Scientific and Technological Research of
˙
˙
Turkey (TÜBITAK-BIDEB), International Research Fellowship
Programme for a grant to N. S., and the French Agence Nationale
de la Recherche (ANR) (ANR-12-BS07-0001-01-RESICAT) for fi-
nancial support.
[1] R. J. P. Corriu, J. P. Masse, J. Chem. Soc., Chem. Commun.
1972, 144–144.
Crystallography: Single crystals of 1·2iPr2O suitable for diffraction
study were obtained by slow diffusion of diisopropyl ether into a
dichloromethane solution of the imidazolium salt. Mr = 2420.88,
[2] K. Tamao, K. Sumitani, M. Kumada, J. Am. Chem. Soc. 1972,
94, 4374–4376.
[3] M. Kumada, Pure Appl. Chem. 1980, 52, 669–679.
[4] K. Tamao, J. Organomet. Chem. 2002, 653, 23–26.
[5] Metal-Catalyzed Cross-Coupling Reactions (Eds.: A. de Mei-
jere, F. Diederich), Wiley-VCH, Weinheim, Germany, 2004.
[6] W. A. Herrmann, in: Homogeneous Catalysis with Organome-
tallic Compounds (Eds.: B. Cornils, W. A. Herrmann), 2nd ed.,
Wiley-VCH, Weinheim, Germany, 2002, p. 91.
[7] J.-P. Corbet, G. Mignani, Chem. Rev. 2006, 106, 2651–2710.
[8] C. Barnard, Platinum Met. Rev. 2008, 52, 38–45.
[9] P. W. N. M. van Leeuwen, P. C. J. Kamer, J. N. H. Reek, P. Di-
erkes, Chem. Rev. 2000, 100, 2741–2769.
[10] J.-C. Hierso, R. Smaliy, R. Amardeil, P. Meunier, Chem. Soc.
Rev. 2007, 36, 1754–1769.
[11] D. Sémeril, M. Lejeune, C. Jeunesse, D. Matt, J. Mol. Catal. A
2005, 239, 257–262.
[12] L. Monnereau, D. Sémeril, D. Matt, L. Toupet, A. J. Mota,
Adv. Synth. Catal. 2009, 351, 1383–1389.
¯
triclinic, space group P1, a = 16.0120(5), b = 19.6770(5), c =
24.2760(8) Å, α = 110.758(3), β = 98.915(3), γ = 105.457(2)°, V =
6624.1(3) Å3, Z = 2, Dx = 1.214 mgm–3, λ(Mo-Kα) = 0.71073 Å, μ
= 0.678 mm–1, F(000) = 2600, T = 120(2) K. Data were collected
with an Oxford Diffraction Xcalibur Saphir 3 diffractometer
(graphite Mo-Kα radiation, λ = 0.71073 Å). The structure was
solved with SIR-97,[36] which revealed the non-hydrogen atoms of
the molecule. After anisotropic refinement, many hydrogen atoms
were located through Fourier difference analysis. The whole struc-
ture was refined with SHELX-97[37] and full-matrix least-square
techniques (use of F2; x, y, z, bij for C, Br, N and O atoms, x, y, z
in riding mode for H atoms); 1495 variables and 15133 observa-
tions with I Ͼ 2.0σ(I); calcd. w = 1/[σ2(Fo2) + (0.1462P)2
+
2
2
13.4589P] where P = (Fo + 2Fc )/3. R1 = 0.0752, wR2 = 0.2657,
Sw = 0.862, Δρ Ͻ 1.188 eÅ–3.
4448
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