反应详情

温度

90 °C

Inside a glove box, Pd(OAc)2 (17.3 mg, 76.9 μmol) and s-Phos [2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl, available from Aldrich] (63.1 mg, 154 μmol) were dissolved in 1,4-dioxane (1 mL). Tripotassium phosphate (9.79 g, 46.1 mmol, 3 eq) was weighed into a 20 mL vial, and 8.59 mL of water was added. 5-Bromo-2-(quinolin-6-yl)benzo[d]oxazole (Precursor 3, 5.00 g, 15.38 mmol) and 1,3-phenylenediboronic acid (1.21 g, 7.30 mmol, 0.475 eq) were dissolved in 55 mL of 1,4-dioxane, and the aqueous tripotassium phosphate solution was added, followed by the catalyst solution. The reaction was stirred at 90° C. for five days. The crude reaction mixture was evaporated to dryness, dissolved in 1 L of boiling chloroform, and adsorbed onto silica gel, followed by rotary evaporation of the solvent. The compound was purified via column chromatography, using an “80 g silica cartridge” and a “2% methanol in chloroform isocratic gradient.” The pure fractions were combined, concentrated, and dried under high vacuum. The compound was received in form of a colorless glass (organic purity: 99.3%). Sublimation on a train sublimator increased the organic purity to 99.6% (1.40 g, 2.47 mmol, 16.1%, colorless microcrystals). 1H-NMR (500 MHz, CDCl3) δ 9.02 (dd, J=4.2, 1.7 Hz, 2H), 8.81 (d, J=2.0 Hz, 2H), 8.61 (dd, J=8.9, 2.0 Hz, 2H), 8.37-8.30 (m, 2H), 8.27 (d, J=8.9 Hz, 2H), 8.14-8.07 (m, 2H), 7.96-7.90 (m, 1H), 7.78-7.58 (m, 7H), 7.52 (dd, J=8.2, 4.2 Hz, 2H); 13C-NMR (126 MHz, CDCl3) δ 110.82, 118.79, 122.13, 125.17, 125.23, 126.52, 126.79, 127.72, 128.01, 128.07, 129.54, 130.55, 136.89, 138.58, 141.71, 142.91, 149.55, 150.68, 152.09, 163.12; ESI/LC/MS/MS: m/z=567 (base peak, [M+H]+), fragmenting into 567, 385, 203, 202, 129, 155, 231. CLogP: 8.434. (ChemBioDraw Ultra, Version 12.0.2.1076, Cambridge-Soft 2010). Additional computed data: HOMO: −5.90 eV, LUMO: −1.93 eV, Triplet Energy: 2.42 eV.

1. customThe crude reaction mixture
2. customwas evaporated to dryness
3. dissolutiondissolved in 1 L of boiling chloroform
4. customfollowed by rotary evaporation of the solvent
5. customThe compound was purified via column chromatography
6. concentrationconcentrated
7. customdried under high vacuum
8. temperatureSublimation on a train sublimator increased the organic purity to 99.6% (1.40 g, 2.47 mmol, 16.1%, colorless microcrystals)