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DOI: 10.1055/s-0030-1258545
Recyclable NHC-Ni Complex Immobilized on Magnetite/Silica Nanoparticles for C-S Cross-Coupling of Aryl Halides with Thiols
Publikationsverlauf
Publikationsdatum:
26. August 2010 (online)
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Abstract
A new type of magnetite/silica nanoparticle-supported N-heterocyclic carbene nickel catalyst (Mag-NHC-Ni) was developed from imidazolium with N-picolyl moieties and used as an efficient catalyst in the C-S coupling of various aryl halides with thiols. Moreover, the catalyst was easily recovered from the reaction mixture by simple filtration and recycled with almost consistent activity.
Key words
heterogeneous catalysis - cross-coupling - magnetic nanoparticle - nickel
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References and Notes
Synthesis of Silica-Coated Magnetic Particles: A two-necked round-bottomed flask (RBF) containing NH4OH (250 mL) and deionized (DI) H2O (250 mL) was vigorously stirred with an overhead stirrer at 500 rpm. A freshly prepared aq solution of iron chloride (100 mL) containing FeCl2˙4H2O (2.57 g, 12.93 mmol) and FeCl3˙6H2O (6.18 g, 22.6 mmol) was dropwise mixed with NH4OH solution for 30 min. The resultant mixture was stirred for additional 1 h at r.t., then the formed MNPs were separated using a magnet (4000 gauss). The MNPs were washed with DI H2O (20 ×) and MeOH (5 ×) by repeating magnet separation and decantation. The MNPs (1.35 g) dried in vacuo were treated with 1% 3-aminopropyltriethoxysilane in CHCl3 (80 mL) at 60 ˚C for 4 h. The aminated MNPs were washed with CHCl3 (10 ×) and MeOH (5 ×) by repeating magnet separation and decantation. The MNPs (1 g) dried in vacuo (elemental analysis, N%: 0.382%, 0.27 mmol/g) were treated with 2% TEOS (tetraethyl orthosilicate) in EtOH and shaken at 30 ˚C for 12 h. The particles were washed with EtOH (6 ×) repeating magnet separation and decantation.
20
Preparation of
Catalyst 5 [MNP-Si-NHC(Pyr)-Ni] and Catalyst 7 [MNP-Si-NHC(Bz)-Ni]:
The aforementioned magnetic nanoparticles (MNPs) were redispersed
in toluene and the resulting solution was heated to reflux. Then,
1-(3-triethoxysilylpropyl)-2-imidazoline was added. After 24 h, the
solution was cooled to r.t. MNPs were concentrated magnetically
by using an external permanent magnet and washed with toluene and
EtOH. Imidazolinyl-functionalized MNPs were redispersed and reacted
with 2-picolyl chloride or benzyl chloride at 80 ˚C in
CHCl3 for 12 h, affording 4 and 6. After washing, the loadings of imidazoles
on MNP-Si were determined by their nitrogen contents by elementary analysis
(4, 0.47 mmol/g; 6,
0.67 mmol/g). The NHC ligand functionalized MNPs were then
redissolved in a mixture
of Ni(acac)2 at 60 ˚C
in DMSO under basic conditions (Scheme
[²]
). After 12 h, the mixture
was cooled to r.t., and then catalyst 5 [MNP-Si-NHC(Pyr)-Ni] or
catalyst 7 [MNP-Si-NHC(Bz)-Ni] were
magnetically separated by using the external magnet. The prepared
catalysts were washed with CHCl3, EtOH, and H2O
subsequently.
General Procedure
for C-S Cross-Coupling Reaction: To a mixture of 10
mol% of catalyst in DMF (1 mL) and Cs2CO3 (2
mmol) were added an aryl halide (1 mmol) and a thiol
(1
mmol). The temperature was raised to 100 ˚C. After 10 h, the
mixture was cooled to r.t. The used catalysts were removed magnetically
by using an external permanent magnet and dried for reuse in the
next round of reactions. The desired products were washed with H2O
and extracted with EtOAc. Then, the organic phase was evaporated
in vacuo and the residues were subjected to flash column chromatography
purification.
After the 4th run, unfortunately the coupling yields were decreased (ca. 10%) and leaching of nickel species was detected from the filtrates after the 4th run and the 5th run (14% and 18%, by ICP-AES analysis of the filtrate).