* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In acetonitrile; at 20℃;Inert atmosphere;
General procedure: In a round-bottomed flask (50 mL) equipped with <strong>[19591-17-4]N-(2-iodophenyl)acetamide</strong> [3] (0.8 g, 3.06 mmol), Pd(PPh3)2Cl2 (0.05 g, 0.08 mmol), CuI (0.03 g, 0.15 mmol) and acetonitrile (20 mL), was added 2-methyl-3-butyne-2-ol (0.33 mL, 3.37 mmol) and Et3N (1.71 mL, 12.25 mmol). The mixture was stirred at room temperature for 6-8 h. Upon completion of the reaction (TLC), the mixture was filtered, the solid residue washed with EtOAc and washings added to the filtrate. The combined solution was concentrated under reduced pressure. The oily material obtained was subjected to column chromatography (hexane/ethyl acetate 4:1) to afford the desired product 1a. Propargyl alcohols 1b-1m were prepared by using the same experimental procedure. Among these compounds, 1a and 1d are known.
1-bromo-2-(((2-phenylbut-3-yn-2-yl)oxy)methyl)benzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
86%
With ferrocenium hexafluorophosphate In dichloromethane at 40℃; for 72h; Inert atmosphere;
1-Bromo-2-(((2-phenylbut-3-yn-2-yl)oxy)methyl)benzene
General procedure: 2-phenyl-3-butyn-2-ol (0.850 g, 5.778 mmol),(2-bromophenyl)methanol (0.721 g, 5.80 mmol), and [Fc]PF6(0.571 g, 0.174 mmol) were added to a evacuated and nitrogenflushed 2 neck round bottom flask and suspended in 20 mL ofCH2Cl2. The reaction was stirred at 40C for 2 days and thenpurified by column chromatography (2 × 30 cm alumina column)using hexane as eluent to give 1-bromo-2-(((2-phenylbut-3-yn-2-yl)oxy)methyl)benzene as a yellow oil (1.269 g, 4.968 mmol, 86%).
benzyl (3-oxo-2-phenylbutan-2-yl) carbonate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
88%
With 1,8-diazabicyclo[5.4.0]undec-7-ene; zinc(II) chloride In acetonitrile at 80℃; for 24h; Autoclave; Sealed tube; chemoselective reaction;
Benzyl 2-Methyl-3-oxobutan-2-yl Carbonate (3a); Typical Procedure (Scheme 2)
General procedure: A 50-mL stainless steel autoclave equipped with a magnetic stir bar was charged with ZnCl2 (27.2 mg, 20 mol%), DBU (76 mg, 50 mol%), 1a (108.1 mg, 1 mmol), 2a (126.1 mg, 1.5 mmol), and CH3CN (2.0 mL) successively and sealed at r.t. The pressure was adjusted to 1 MPa with CO2 at the preset temperature (80 °C) and the autoclave was heated at that temperature for 24 h. After the reaction was complete, the reactor was cooled in ice-water bath, and then excess CO2 was carefully vented. After reaction, the crude mixture was further purified by column chromatography (silica gel, petroleum ether/EtOAc 50:1-10:1) to provide 3a as a colorless liquid; yield: 219 mg (92%); Rf = 0.41 (hexane/EtOAc 10:1).
86%
With triphenylphosphine; silver carbonate In acetonitrile at 80℃; for 18h; Autoclave;
50 %Spectr.
With DBN In N,N-dimethyl-formamide at 50℃; for 6h;
With 1,8-diazabicyclo[5.4.0]undec-7-ene; zinc(II) chloride In acetonitrile at 80℃; for 24h; Autoclave; Sealed tube; chemoselective reaction;
4-Methyl-1,3-dioxolan-2-one (5a); Typical Procedure (Table 2)
General procedure: A 50-mL stainless steel autoclave equipped with a magnetic stir bar was charged with ZnCl2 (27.2 mg, 20 mol%), DBU (76 mg, 50 mol%), 4a (76.1 mg, 1 mmol), 2a (126.1 mg, 1.5 mmol), and CH3CN (2.0 mL) successively and sealed at r.t. The pressure was adjusted to 1 MPa with CO2 at the preset temperature (80 °C) and the autoclave was heated at this temperature for 24 h. After the reaction was complete, the reactor was cooled in ice-water bath, and then excess CO2 was carefully vented. The mixture was diluted with EtOAc, and the yield of cyclic carbonate 5a and α-hydroxy ketone 6a was determined by gas chromatograph (Agilent 6890) equipped with a capillary column (HP-5 30 m * 0.25 µm) using a flame ionization detector using biphenyl (40 mg) as the internal standard. Then, the residue was obtained by removing the solvent under vacuum and further purified by column chromatography (petroleum ether/EtOAc 100:1-5:1) to obtain 5a and 6a.
With tetrakis(triphenylphosphine) palladium(0); copper(II) iodide; triethylamine In acetonitrile at 80℃; for 1.5h;
Methyl 6-amino-5-(4-hydroxy-4-methylpent- 1 -yn-1 - yl)pyridine-3-carboxylate
General procedure: To 0.40 g (1.73 mmol) methyl 6-amino-5-bro- mopyridine-3-carboxylate and 0.22 g (2.25 mmol) 2-meth- ylpent-4-yn-2-ol in 8 mE ACN are added 0.84 mE (6.06 mmol) TEA, 33.0 mg (0.17 mmol) Cu(I)I and 0.20 g (0.17 mmol) tetrakis(triphenylphosphine)-palladium(0) and the reaction mixture is stirred at 80° C. for 1 h. Afier cooling down to RT the reaction mixture is diluted with EtOAc and washed with a mixture of sat. aq. NH4C1 solution and ammonia (9:1), the organic layer is dried over a phase separator cartridge and the solvent is removed in vacuo. The remaining crude product is purified by column chromatography (silica gel; CyR/EtOAc 9/1) to obtain the product.
With copper(l) iodide; sodium azide; sodium L-ascorbate; potassium hydroxide; In water; toluene; at 80℃; for 0.25h;Microwave irradiation;
General procedure: Arylboronic acid 1 (0.3 mmol), but-3-yn-2-ol 2(0.36 mmol), sodium azide 3 (0.36 mmol), KOH(0.9 mmol), CuI (0.015 mmol), NaAsc (0.03 mmol),and PhMe-H2O (2 mL, 5:1 in volume) were added to amicrowave reaction tube. The mixture was conductedunder microwave at 80 C for 15 min. After thereaction completed by TLC analysis, H2O (25 mL)was added to the mixture and the system was extractedwith EtOAc (3 9 20 mL). The combined organic layerwas washed with brine (3 9 5 mL), dried withNa2SO4, and concentrated under reduced pressure toafford the crude product. Purification by columnchromatography on silica gel with EtOAc-PE (1:5)afforded the desired product 4.
Chemistry
Pharmaceutical Intermediates
Inhibitors/Agonists
Material Science
For Research Only
110K+ Compounds
Competitive Price
1-2 Day Shipping
