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1 IICT communication No. 060818.
9
Preparation of NAP-Mg-Pd(0) Catalyst:
[5c]
NAP-MgO (1 g, BET 600 m2/g, purchased from NanoScale Materials Inc., Manhattan, USA) was treated with Na2PdCl4 (294 mg, 1 mmol) dissolved in decarbonated H2O (100 mL) and the resulting mixture was stirred for 12 h under a nitrogen atmosphere to afford the brown colored NAP-Mg-PdCl4. Then the catalyst was filtered, washed with deionized H2O and acetone, and dried. Then NAP-Mg-PdCl4
(1g) was reduced with hydrazine hydrate (1 g, 20 mmol) in anhyd EtOH (20 mL) for 3 h under a nitrogen atmosphere to give the black colored air-stable NAP-Mg-Pd(0) (Pd 0.99
mmol/g).
Heck Coupling of Iodo and Bromoarene: 4-Bromoanisole (2 mmol), styrene (2.2 mol), NaOAc (6 mmol), dimethyl-acetamide (DMAc, 5 mL), and NAP-Mg-Pd(0) (0.1 mol%) were taken in a 20-mL reaction vessel and stirred under a nitrogen atmosphere at 135 °C (monitored by GC). After completion of the reaction the catalyst was separated by filtration, washed with H2O and acetone, and dried in air. The filtrate was diluted with Et2O and washed with H2O. The organic layer was concentrated to give the crude product, which was purified by column chromatography (hexane-EtOAc, 9:1) to give pure 4-methoxy-trans-stilbene in 94% yield (395 mg); mp 135-137 °C. 1H NMR (300 MHz, CDCl3): δ = 3.84 (s, 3 H), 6.81-7.07 (m, 4 H), 7.17-7.53 (m, 7 H). EI-MS: m/z (%) = 210 (M+), 195, 167, 165, 152. Anal. Calcd for C15H14O: C, 85.68; H, 6.71. Found: C, 85.45; H, 6.83.
Heck Coupling of Chloroarenes: 4-Chloroacetophenone (2 mmol), styrene (2.2 mol), NaOAc (6 mmol), TBAB (2 mmol), DMAc (5 mL), and NAP-Mg-Pd(0) (1.0 mol%) were taken in a 20-mL reaction vessel and stirred under a nitrogen atmosphere at 135 °C (monitored by GC). After completion of the reaction the catalyst was separated by filtration, washed with H2O and acetone, and dried in air. The filtrate was diluted with Et2O and washed with a solution of 1% HCl (to remove the amine formed from decomposition of TBAB) and then a sat. solution of NaCl. Then organic layer was dried over Na2SO4 and concentrated to get the crude product, which was purified by column chromatography (hexane-EtOAc, 8:2) to give pure 4-acetyl-trans-stilbene in 92% yield (408 mg); mp 134-136 °C. 1H NMR (300 MHz, CDCl3): δ = 2.6 (s, 3 H), 7.12 (d, J = 16.6 Hz, 1 H), 7.22 (d, J = 16.6 Hz, 1 H), 7.28-7.41 (m, 3 H), 7.53 (d, J = 6.8 Hz, 2 H), 7.59 (d, J = 8.3 Hz, 2 H), 7.95 (d, J = 8.3 Hz, 2 H). EI-MS: m/z = 222 (M+), 207, 178, 149, 77, 51, 43. Anal. Calcd for C16H14O: C, 86.45; H, 6.35. Found: C, 86.28; H, 6.47.
Sonogashira Reaction: 4-Bromoanisole (0.5 mmol), phenylacetylene (0.6 mol), Et3N (1 mmol), DMF (3 mL), and NAP-Mg-Pd(0) (1.0 mol%) were taken in a 10-mL reaction vessel and stirred under a nitrogen atmosphere at 75 °C (monitored by GC). After completion of the reaction, the catalyst was separated by filtration, washed with H2O and acetone, and dried in air. The filtrate was diluted with Et2O and washed with a sat. solution of NaCl. The organic layer was concentrated to give the crude product, which was purified by column chromatography(hexane) to give pure 4-methoxydiphenylacetylene in 92% yield (96 mg); mp 55-57 °C. 1H NMR (300 MHz, CDCl3): δ = 3.8 (s, 3 H), 6.83 (d, J = 8.3 Hz, 2 H), 7.25-7.35 (m, 3 H), 7.39-7.51 (m, 4 H). EI-MS: m/z = 208 (M+), 194, 167, 166, 140. Anal. Calcd for C15H12O: C, 86.51; H, 5.81. Found: C, 86.39; H, 5.96.