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DOI: 10.1055/s-0030-1259310
In Situ Generation of Palladium Nanoparticles: Reusable, Ligand-Free Heck Reaction in PEG-400 Assisted by Focused Microwave Irradiation
Publikationsverlauf
Publikationsdatum:
13. Januar 2011 (online)
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Abstract
A rapid and efficient Heck coupling reaction of aryl iodides with terminal olefins was conducted in PEG-400 at 120 ˚C in the presence of potassium carbonate and palladium nanoparticles formed in situ from palladium chloride under focused microwave irradiation. High to excellent product yields were achieved. The reaction medium and catalyst could be easily recycled at least five times without significant loss in reactivity.
Key words
Heck reaction - ligand-free palladium catalysis - palladium nanoparticles - focused microwave irradiation - PEG-400 - green chemistry
- Supporting Information for this article is available online:
- Supporting Information
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References and notes
General Procedure
for the Heck Coupling Reactions of Aryl Iodides with Terminal Olefins:
In a 10-mL glass tube were placed aryl iodide (0.5 mmol), terminal
olefin (0.6 mmol), K2CO3 (1.0 mmol), PdCl2 (0.005
mmol), PEG-400 (3 mL), and a magnetic stir bar. The vessel was sealed
with a septum and placed into the microwave cavity. Microwave irradiation
of 10 W was used, and the temperature was ramped from r.t. to 120 ˚C.
Once the temperature of
120 ˚C was reached, the
reaction mixture was held at this temperature for 12 min. After
cooling the mixture to r.t., the reaction vessel was opened, the
contents were extracted with Et2O (5 × 5 mL;
for substrates with carboxyl group, acidification using hydrochloric
acid was needed before extraction) and the combined organic layers
were dried over anhyd MgSO4. The solvent was removed
by evaporation under reduced pressure to afford the crude products,
which were further purified by recrystallization or by column chromatography
on silica gel using petroleum ether and EtOAc as eluent. The catalyst
system (Pd-PEG) was recycled by the evaporation of Et2O
and H2O under reduced pressure and could be reused directly
in the next run.
Selected Data for
Compound 1a: white crystal; mp 133-134 ˚C. ¹H
NMR (400 MHz, CDCl3): δ = 12.13 (s,
1 H), 7.82 (d, J = 16.0 Hz,
1 H), 7.54-7.56 (m, 2 H), 7.39-7.43 (m, 3 H),
6.47 (d, J = 16.0 Hz, 1 H). ¹³C
NMR (100 MHz, CDCl3): δ = 172.75, 147.12,
133.99, 130.75, 128.95, 128.36, 117.30. MS (EI): m/z = 148 [M+],
105, 77. IR: 1682, 1628, 1419, 767, 705 cm-¹.
Anal. Calcd for C9H8O2 (148.05):
C, 72.96; H, 5.44. Found: C, 72.64; H, 5.38.