* 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.
Reference：
[1] Green Chemistry, 2017, vol. 19, # 8, p. 1983 - 1989
2
[ 340322-86-3 ]
[ 84284-70-8 ]
Yield
Reaction Conditions
Operation in experiment
99%
With potassium carbonate In tetrahydrofuran; methanol at 20℃; for 12 h;
A solution of 23 (5.9 g, 21 mmol) and K2CO3 (10.2 g, 73.4 mmol) in dry methanol (30 mL) and THF (30 mL) was stirred at rt for 12 h. The reaction mixture was filtered off and the filtrate was evaporated under reduced pressure. The crude product was dissolved in ethyl acetate and washed with water. The organic layer was dried over Na2SO4 and evaporated in vacuum to get a white crystal (4.43 g, 99percent). Mp 65-66 °C 21; 1H NMR (500 MHz, CDCl3) δ 7.63-7.42 (m, 7H), 6.95 (d, J=8.5 Hz, 2H), 5.10 (s, 2H), 3.05 (s, 1H); 13C NMR (125 MHz, CDCl3) δ 159.1, 138.7 (2×C), 134.1, 129.1 (2×C), 128.6, 127.9 (2×C), 117.7 (2×C), 115.3, 83.5, 76.3.
Reference：
[1] ChemMedChem, 2010, vol. 5, # 8, p. 1236 - 1241
[2] Tetrahedron, 2014, vol. 70, # 47, p. 9084 - 9092
[3] European Journal of Organic Chemistry, 2017, vol. 2017, # 24, p. 3457 - 3460
[4] Organic Letters, 2014, vol. 16, # 3, p. 948 - 951
[5] Bioorganic and Medicinal Chemistry, 2005, vol. 13, # 7, p. 2637 - 2649
[6] Patent: US2006/46977, 2006, A1, . Location in patent: Page/Page column 17
3
[ 114943-73-6 ]
[ 84284-70-8 ]
Yield
Reaction Conditions
Operation in experiment
95.5%
Stage #1: With lithium diisopropyl amide In tetrahydrofuran; n-heptane; ethylbenzene at -78℃; for 2 h; Stage #2: With ammonium chloride In tetrahydrofuran; n-heptane; ethylbenzene
General procedure: Lithium diisopropylamide solution (2 M in heptane/THF/ethylbenzene, 5 equiv) was slowly added to appropriate 2,2-dibromo-vinyl derivatives 40a3-d3 (1 equiv), dissolved in dry THF at -78 oC. The temperature was kept at -78 oC, and the mixture was stirred for 2 h. The reaction was quenched with saturated NH4Cl solution and extracted with CH2Cl2. The combined organic solutions were dried over Na2SO4 and concentrated in vacuo. The residue was purified by silica gel flash column chromatography.
68%
With caesium carbonate In dimethyl sulfoxide at 110℃;
(b) 4-Ethynyl-1-(phenylmethoxy)benzene (3) To a solution of the compound 2 (8.29 g, 22.7 mmol) in dimethylsulfoxide (DMSO, 100 mL) was added Cs2CO3 (22.2 g, 68.0 mmol) and heated to 110° C. overnight. Then the reaction mixture was cooled to room temperature and poured into water (500 mL), and extracted with ethyl acetate (2*300 mL). The combined organic layers were washed with brine (500 mL), dried over Na2SO4, and concentrated in vacuo. The residue was purified by silica gel column chromatography (petroleum ether/ethyl acetate=50:1) to afford the compound 3 (3.17 g, yield: 68percent) as a white solid. 1H NMR (CDCl3, 300 MHz): δ 3.00 (s, 1H), 5.07 (s, 2H), 6.90-6.94 (m, 2H), 7.33-7.455 (m, 7H).
Reference：
[1] Bioorganic and Medicinal Chemistry Letters, 2009, vol. 19, # 11, p. 3125 - 3127
[2] European Journal of Medicinal Chemistry, 2011, vol. 46, # 6, p. 2386 - 2396
[3] Tetrahedron Letters, 2011, vol. 52, # 9, p. 992 - 994
[4] Patent: US2015/322033, 2015, A1, . Location in patent: Paragraph 0112; 0115; 0116
Stage #1: With triphenylphosphine In dichloromethane at 0 - 20℃; for 0.5 h; Stage #2: With lithium diisopropyl amide In tetrahydrofuran; n-heptane; ethylbenzene at -78℃; for 2 h; Stage #3: With ammonium chloride In tetrahydrofuran; n-heptane; ethylbenzene
General procedure: PPh3 (4 equiv) was added at 0 oC to a solution of CBr4 (2 equiv) in dry CH2Cl2. At the same temperature, the appropriate aldehyde 40a2-d2 (1 equiv) dissolved in dry CH2Cl2 was dropped slowly into the reaction mixture. The cooling bath was removed and the reaction mixture was stirred at room temperature. After 30 min, water was added and the contents of the aqueous phase were extracted with CH2Cl2. The combined organic phases were dried over Na2SO4 and concentrated. The residue was purified by silica gel flash column chromatography.; General procedure: Lithium diisopropylamide solution (2 M in heptane/THF/ethylbenzene, 5 equiv) was slowly added to appropriate 2,2-dibromo-vinyl derivatives 40a3-d3 (1 equiv), dissolved in dry THF at -78 oC. The temperature was kept at -78 oC, and the mixture was stirred for 2 h. The reaction was quenched with saturated NH4Cl solution and extracted with CH2Cl2. The combined organic solutions were dried over Na2SO4 and concentrated in vacuo. The residue was purified by silica gel flash column chromatography.
Reference：
[1] European Journal of Medicinal Chemistry, 2011, vol. 46, # 6, p. 2386 - 2396
With 1,4-diisocyanatobenzene; triethylamine; In toluene; at 110℃; for 6h;
(b) 3-[3-(4-Benzyloxyphenyl)-4-bromoisoxazol-5-yl]propionic acid; 1,4-Phenylenediisocyanate (19.95 g, 124.56 mmol) and triethylamine (26.0 mL, 186.73 mmol) were added to a solution of 1-(benzyloxy)-4-ethynylbenzene (12.97 g, 62.28 mmol) and <strong>[13013-02-0]4-nitrobutanoic acid methyl ester</strong> (13.74 g, 93.42 mmol) in toluene (700 mL). The obtained mixture was stirred at 110C for 6 hours. The reaction solution was filtered with celite, and the solvent was then distilled away. The residue was washed with diisopropyl ether to obtain an isoxazole compound (14.50 g, yield: 69%) in the form of a colorless powder. N-Bromosuccinimide (15.37 g, 86.33 mmol) was added to a solution of the obtained isoxazole compound (27.73 g, 82.22 mmol) in DMF (220 mL) at room temperature, and the obtained mixture was then stirred for 5.5 hours. Thereafter, water (70 mL) was added to the reaction solution, and the precipitated crude crystals were collected by filtration, so as to obtain a bromo compound in the form of a grayish powder. The obtained bromo compound was dissolved in a mixture of methanol (400 mL) and THF (100 mL), and a 3 M-sodium hydroxide aqueous solution (55 mL, 165 mmol) was then added to the solution. The obtained mixture was stirred at 60C for 1.5 hours. Thereafter, 5 M hydrochloric acid was added to the reaction solution to make it acidic, and the precipitated crude crystals were collected by filtration, so as to obtain the title compound (32.20 g, yield in two steps: 97%) in the form of a colorless powder. 1H NMR (400 MHz, CDCl3): delta (ppm) = 7.97 (2H, d, J = 8.8 Hz), 7.45-7.33 (5H, m), 7.08 (2H, d, J = 8.8 Hz), 5.13 (2H, s), 3.03 (2H, t, J = 8.3 Hz), 2.91 (2H, t, J = 8.3 Hz).
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; sodium L-ascorbate; diisopropylamine; In tetrahydrofuran; at 40℃; for 16h;Inert atmosphere;
General procedure: Compound 24 (150 mg, 0.80 mmol) in THF (5 mL) was stirredwith CuI (15.2 mg, 80 lmol) and (Ph3P)2PdCl2 (28 mg, 40 lmol)in Pri2NH (5 mL) under Ar at 45 C for 30 min. Phenylethyne 21a(163 mg, 1.6 mmol) was added. The mixture was stirred at 40 Cfor 5 d. Evaporation and chromatography (petroleum ether/EtOAc3:1) gave 25a (80 mg, 50%) as a pale buff powder.
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