Organometallics
ARTICLE
JEOL ECX-400 spectrometer and were referenced to residual protio
solvent peaks. Melting points were measured on an Electrothermal Mel-
temp melting point device.
experiments. This material is available free of charge via the
General Procedure for the Copper-Catalyzed Conversion
of Aryl Bromides into Aryl Iodides. In a nitrogen-filled glovebox,
CuI (15 mg, 0.079 mmol, 5 mol %), NaI (450 mg, 3.00 mmol), and an aryl
bromide (1.5 mmol) were weighed into an oven-dried microwave tube
containing a small stir bar. Acetonitrile (0.6 mL) was added by syringe.
Then trans-N,N0-dimethylcyclohexane-1,2-diamine (23.7 μL, 0.1 mmol,
10 mol %) was added by positive displacement pipet, the sample was
stirred, and a septum-lined cap was added. The initial reaction mixture
appeared as a yellow or yellow-green liquid over a white solid. After
removing the tube from the box, the reaction was performed in a CEM
Discover microwave reactor for 30ꢀ120 min at 100 °C and 250 W (with
power adjustments to maintain temperature), with a 2 min ramp time.
Aftercooling, thereaction mixture containeda turquoise-blueliquid overa
solid. After cooling, the product mixture was purified by column
chromatography on silica. The yields reported did not take into account
the trace amount of aryl bromide present in the isolated products.
General Procedure for the Copper-Catalyzed Conversion
of Aryl Chlorides into Aryl Iodides. In a nitrogen-filled glovebox,
CuI (10 mg, 0.047 mmol, 5 mol %), NaI (300 mg, 2.00 mmol), and an
aryl chloride (1.0 mmol) were weighed into an oven-dried microwave
tube containing a small stir bar. Acetonitrile (0.5 mL) was added by
syringe. Then trans-N,N0-dimethylcyclohexane-1,2-diamine (23.7 μL,
0.1 mmol, 10 mol %) was added by positive displacement pipet, the
sample was stirred, and a septum-lined cap was added. The initial
reaction mixture appeared as a yellow or greenish liquid over a white
solid. After removing the tube from the box, the reaction was performed
in a CEM Discover microwave reactor for 60 min at 200 °C and
250 W (with power adjustments to maintain temperature), with a 2 min
ramp time. After cooling, the crude reaction mixture appeared as a
yellow or brown solution. An equimolar amount (versus ArCl) of either
hexadecane or decane was added to the solution. The solution was then
quenched with 2 mL of water and 2 mL of EtOAc. The resulting solution
was a dark brown, cloudy organic layer over a purple aqueous layer. A
drop was removed from the organic layer and diluted with 10 drops of
EtOAc in order to determine the GC yield.
General Procedure for the Copper-Catalyzed Conversion
of Aryl Bromides and Aryl Chlorides into Arenes. In a nitrogen-
filled glovebox, CuI (40 mg, 0.21 mmol, 20 mol %), NaI (300 mg,
2.00mmol, 2 equiv), and anarylbromide orarylchloride (1.0 mmol) were
weighed into an oven-dried microwave tube containing a small stir bar.
Acetonitrile (0.5 mL) was added by syringe. Then trans-N,N0-dimethyl-
cyclohexane-1,2-diamine (237 μL, 1.5 mmol, 1.5 equiv) was added by
positive displacement pipet, the sample was stirred, and a septum-lined
cap was added. The initial reaction mixture appeared as a yellow or
greenish liquid over a white solid. After removing the tube from the
drybox, thereactionwas performed ina CEM Discover microwave reactor
for 1ꢀ2 h at 200 °C and 250ꢀ300 W (with power adjustments to
maintain temperature), with a 5ꢀ10 min ramp time. Most reactions
reached 200 °C after ∼2 min. After the desired reaction time was reached
and the tube cooled, the crude reaction mixture appeared as a dark brown
liquid over some solids. The product mixture was either spiked with
∼1.0 mmol of decane for GC yield determination or purified by column
chromatography on silica gel. Products purified by column chromatogra-
phy routinely contained a small percentage of the corresponding aryl
iodide, measurable by GC and/or NMR and reported yields were
adjusted to account for this impurity.
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: lin@usna.edu.
’ ACKNOWLEDGMENT
K.A.C., M.E.G., and C.K.K. gratefully acknowledge the Office
of Naval Research for partial support of this work on funding
document NN00014110WX30241. S.L. would like to thank
Research Corporation Cottrell College Science Award. A.H.R.M.
would like to thank the Naval Academy Research Council and the
Office of Naval Research for partial support of this work on
funding document N0001409WR40059.
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’ ASSOCIATED CONTENT
S
Supporting Information. Characterization data for all
b
isolated products and experimental details for deuterium-labeling
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dx.doi.org/10.1021/om2003706 |Organometallics 2011, 30, 4067–4073