Armelle Ouali et al.
FULL PAPERS
pure and dry nitrogen atmosphere. Acetonitrile was distilled
from P4O10 and was stored on 4 activated molecular sieves
under a nitrogen atmosphere. Cesium carbonate (Aldrich)
on MgSO4, filtered and concentrated under vacuum to yield
the crude product which was purified by silica gel chromatog-
raphy with an eluent of hexanes and dichloromethane. The
products were characterized by 1H NMR, 13C NMR and mass
spectra comparisons with those of authentic samples.
¨
and tripotassium phosphate (Riedel-de Haen) were ground
to a fine powder and stored under vacuum in the presence of
P4O10. All other solid materials were stored in the presence
of P4O10 in a bench-top desiccator under vacuum at room tem-
perature and weighed in the air. Copper(I) iodide was purified
according to literature procedures[14] and stored protected
from light. The synthesis of ligand 1 was reported in our previ-
ous papers.[9a, c] Iodobenzene, aryl bromides and phenols were
purchased from commercial sources (Aldrich, Acros, Avoca-
do, Fluka, Lancaster). If solids, they were recrystallized in an
appropriate solvent.[15] If liquids, they were distilled under vac-
uum and stored under an atmosphere of nitrogen. Special care
was taken with iodobenzene which was regularly distilled and
stored protected from light. All phenols were also stored pro-
tected from light.
Acknowledgements
We thankRHODIAOrganique Fine and CNRS for a PhD grant
and financial support.
References and Notes
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Column chromatography was performed with SDS 60A C.C
silica gel (35–70 mm). Thin layer chromatography was carried
out using Merck silica gel 60F 254 plates.
All products were characterized by their 1H NMR, 13C NMR
and GC/mass spectra. NMR spectra were recorded at 208C on
a Bruker AC 200 MHz or on a DRX-250 spectrometer working
1
respectively at 200.13 and 250.13 MHz for H, at 50.32 and
62.90MHz for 13C and at 188.31 and 236.36 for 19F. Gas chroma-
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Technologies 6890N instrument with an Agilent 5973 N mass
detector (EI) and a HP5-MS 30m ꢀ0.25 mm capillary apolar
column (stationary phase: 5% diphenyldimethylpolysiloxane
film, 0.25 mm). GC/MS method: initial temperature: 458C; ini-
tial time: 2 min; ramp: 28C/min until 508C then 108C/min; final
temperature: 2508C; final time: 10min. Melting points were
determined using a Büchi B-540apparatus and are uncorrect-
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General Procedure for Copper-Catalyzed Coupling
Reaction of Phenols and Aryl Bromides (2-mmol
Scale)
After standard cycles of evacuation and back-filling with dry
and pure nitrogen, an oven-dried Radley tube (Carousel “reac-
tion stations RR98030”) equipped with a magnetic stirring bar
was charged with CuI (38.1 mg, 0.2 mmol), ligand 1 (29.2 mg,
0.1 mmol), the phenol (3.0 mmol), K3PO4 (848 mg, 4.0mmol)
and the aryl bromide (2.0mmol), if a solid. The tube was evac-
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added under a stream of nitrogen by syringe at room tempera-
ture, followed by anhydrous and degassed acetonitrile
(1.2 mL). The tube was sealed under a positive pressure of ni-
trogen, stirred and heated to 60or 80 8C for the required time
period. After cooling to room temperature, the mixture was di-
luted with diethyl ether (~20mL) and filtered through a plug of
celiteꢂ, the filter cake being further washed with diethyl ether
(~5 mL). The filtrate was washed twice with water (~10mL ꢀ
2). Gathered aqueous phases were twice extracted with di-
chloromethane (~10mL). Organic layers were gathered, dried
´
f) R. F. Pellon, R. Carrasco, V. Milian, L. Rodes, Synth.
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504
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Adv. Synth. Catal. 2006, 348, 499 – 505