With copper(II) sulfate hydrate; potassium hydroxide In water at 20℃; for 24 h;
General procedure: A flask was charged with 3,4-dimethoxyphenylboronic acid (1.0 mmol),CuSO4*H2O (0.02 g, 0.1 mmol), CNT-Chit film (10.0 mg), KOH (0.17 g, 3.0mmol), and H2O (5.00 mL). Then, the flask was stirred at room temperature in open air for 24 hours. At the end of the reaction, the reaction mixture was filtered and washed with water. Then, the filtrate was acidified with dilute aqueous HCl and extracted with diethyl ether (3 10 mL). The organic phases were combined, and the volatile components were evaporated under reduced pressure. Purification by flash column chromatography on silica gel (70percenthexanes/ 30percent ethyl acetate) afforded 0.1433 g of 3,4-dimethoxyphenol (2f) in 93percent isolated yield as an off-white solid
Reference：
[1] Tetrahedron Letters, 2018, vol. 59, # 52, p. 4597 - 4601
[2] Journal of the American Chemical Society, 2018, vol. 140, # 13, p. 4623 - 4631
[3] Organic Letters, 2012, vol. 14, # 13, p. 3494 - 3497
[4] Journal of Medicinal Chemistry, 2014, vol. 57, # 6, p. 2536 - 2548
[5] Advanced Synthesis and Catalysis, 2018, vol. 360, # 10, p. 2013 - 2019
2
[ 5332-24-1 ]
[ 191162-39-7 ]
Yield
Reaction Conditions
Operation in experiment
90%
With n-butyllithium; Triisopropyl borate In tetrahydrofuran; hexane at -78℃; for 1 h; Inert atmosphere; Schlenk technique
General procedure: To a two-neck 250mL round bottom flask, triisopropyl borate (3.30mL, 29.06mmol) and 3-bromoquinoline (3.00g, 14.49mmol) was dissolved in dry THF (100mL), then n-butyllithium (14.50mL of a 2M solution in hexane, 29.00mmol) was added dropwise via a dropping funnel over 1h under N2 at−78°C. After 2h, the acetone/dry ice bath was removed, and the reaction solution was allowed to warm to 0°C. The reaction was then quenched with a 2M HCl solution, and the pH value was adjusted to 7 with a solution of 2M NaHCO3. The resulting solution was extracted with ethyl acetate (EA) (3×100mL). The combined organic layers were dried with MgSO4 and evaporated to dryness. n-Hexane was then added to precipitated the product as a white solid (80percent yield).
Reference：
[1] Dyes and Pigments, 2013, vol. 99, # 1, p. 105 - 115
[2] Synthetic Communications, 2003, vol. 33, # 5, p. 795 - 800
[3] Journal of Organic Chemistry, 2002, vol. 67, # 15, p. 5394 - 5397
[4] Patent: US2009/181941, 2009, A1, . Location in patent: Page/Page column 49-50
[5] Journal of the American Chemical Society, 2012, vol. 134, # 28, p. 11667 - 11673
[6] Organic Letters, 2012, vol. 14, # 18, p. 4814 - 4817,4
3
[ 5332-24-1 ]
[ 5419-55-6 ]
[ 191162-39-7 ]
Yield
Reaction Conditions
Operation in experiment
72%
Stage #1: With n-butyllithium In tetrahydrofuran at -75 - 0℃; for 0.333333 h; Stage #2: With hydrogenchloride; water In tetrahydrofuran
Compound 3-bromo-quinoline (3-bromoquinoline) 10g (48.06mmol) and triisopropylborate (triisopropylborate) 22mL (96.13mmol) dissolved in 200mL of THF and then, at -75 ° C n-BuLi 53mL (96.13mmol) of It was added slowly. After stirring at ° C or less for 20 minutes into the 2N HCl, it was adjusted to pH 7 neoteumyeonseo a 5NNaOH slowly. Ethyl acetate (Ethyl acetate) and was extracted with distilled water,methanol and recrystallization conducted by removing water to give the title compound21-45.95g (72percent).
56%
With n-butyllithium In tetrahydrofuran; hexane at -78 - -20℃;
To a solution of compound 3-bromoquinoline (2.08 g, 10 mmol), triisopropyl borate (2.3g, 12 mmol) in THF (20 mL) was added n-BuLi (4 mL, 2.5 M in hexane) at -780C. The reaction mixture was stirred for 1 h at -780C, then warmed to -200C and quenched with 2 N HCl (50 mL, 100 mmol). The mixture was concentrated and purification by chromatography (MeOH:DCM=l : 10) to give quinolin-3-ylboronic acid (0.97g, 56percent) as light yellow solid. MS (M/Z) M*+H): M"+H=174
Reference：
[1] Patent: KR2016/52399, 2016, A, . Location in patent: Paragraph 0151-0154
[2] Patent: WO2009/155527, 2009, A2, . Location in patent: Page/Page column 134
[3] Chemistry - A European Journal, 2014, vol. 20, # 1, p. 263 - 271
4
[ 5332-24-1 ]
[ 121-43-7 ]
[ 191162-39-7 ]
Yield
Reaction Conditions
Operation in experiment
34%
With sodium hydroxide; n-butyllithium In hexane; di-isopropyl ether; acetic acid; ethyl acetate
PREPARATION 98 Quinolin-3-ylboronic Acid A 2.5M solution of n-butyllithium in hexane (4.4 ml, 11 mmol) was slowly added to a stirred solution of 3-bromoquinoline (2.08 g, 10 mmol) in anhydrous ether (20 ml), under nitrogen, at -75° C. After a further 20 minutes at -75° C., trimethylborate (1.46 ml, 13 mmol) was added, whereupon the red colour changed to yellow. The reaction mixture was allowed to warm to room temperature and quenched with water, followed by 1M aqueous sodium hydroxide solution (10 ml). The resulting mixture was stirred for 30 minutes and then glacial acetic acid added until a pH ~5-6 was attained, which generated a gummy precipitate. Diisopropyl ether was added to this mixture, stirring continued for 1 hour and then the clear aqueous and organic phases were decanted from the solid and discarded. The solid residue was dissolved in ethyl acetate and the solution washed with water, dried (MgSO4) and evaporated under reduced pressure to give the title compound as a pale yellow solid (580 mg, 34percent). Found: C, 62.74; H, 4.11; N, 7.92. C9H8BNO2 requires C, 62.49; H, 4.66; N, 8.10percent. δ(DMSOd6): 7.59 (t,1H), 7.76 (t,1H), 7.98 (m,2H), 8.42 (brs,2H,exchangeable), 8.70 (s,1H), 9.18 (s,1H).
With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; ethanol; water; at 90℃;
General synthetic scheme for BA112, BA115, BA121, BA122, BA124, BA136, BA138. BA141, and BA144. A solution of boronic acid (2.5 equivalents) in EtOH (1.65 ml) was added to a solution of 1-cyclopentyl-3-iodo-1H-pyrazolo[3,4-d]pyrimidin-4-amine (BA80, 1 equivalent) in DME (6 ml). Pd(PPh3)4 (15 mg, 0.15 mmol) and saturated Na2CO3 (0.95 ml) were added and the reaction was heated to 90 C. under an argon atmosphere overnight. After cooling, the reaction was extracted with saturated NaCl and CH2Cl2. Organic phases were combined, concentrated in vacuo and purified by RP-HPLC (MeCN:H2O:0.1% TFA) to yield desired products. Products were analyzed by LC-MS.
With potassium phosphate; chloro(2-dicyclohexylphosphino-2‘,4’,6’-triisopropyl-1,1‘-biphenyl)[2-(2’-amino-1,1‘-biphenyl)]palladium(II); tetrabutylammomium bromide In 1-methyl-pyrrolidin-2-one; water; toluene at 90℃; Flow reactor;
With sodium carbonate In 1,4-dioxane; water at 100℃; for 3h; Inert atmosphere;
1.1.4
Example 1(4)3-{3-(Trifluoromethyl)-1H-pyrazolo[3,4-b]pyridin-4-yl}quinoline (1d)A [1,1-bis-(diphenylphosphino)-ferrocene]dichloropalladium(II) dichloromethane complex (0.74 g) was added to a solution of compound (1c) (2.0 g), quinoline-3-boronic acid (2.5 g), and an aqueous sodium carbonate solution (1 M, 18 mL) in 1,4-dioxane (45 mL) under a nitrogen atmosphere, followed by stirring at 100° C. for 3 hr. The reaction solution was distributed between ethyl acetate and water, and the organic layer was washed with saturated saline and then dried over anhydrous sodium sulfate. After distillation of the solvent, the residue was purified by neutral silica gel column chromatography (chloroform/methanol) to obtain compound (1d) (0.94 g, 33%) as a white solid.1H-NMR (DMSO-d6) δ 14.89 (1H, brs), 9.00 (1H, d, J=2.0 Hz), 8.81 (1H, d, J=4.6 Hz), 8.54 (1H, d, J=2.0 Hz), 8.14 (1H, d, J=8.2 Hz), 8.08 (1H, d, J=8.2 Hz), 7.88 (1H, td, J=6.9, 1.5 Hz), 7.72 (1H, brt, J=6.9 Hz), 7.51 (1H, d, J=4.6 Hz); LRMS (ESI) m/z 315 [M+H]+.
With copper(II) sulfate hydrate; potassium hydroxide; In water; at 20℃; for 24h;
General procedure: A flask was charged with 3,4-dimethoxyphenylboronic acid (1.0 mmol),CuSO4*H2O (0.02 g, 0.1 mmol), CNT-Chit film (10.0 mg), KOH (0.17 g, 3.0mmol), and H2O (5.00 mL). Then, the flask was stirred at room temperature in open air for 24 hours. At the end of the reaction, the reaction mixture was filtered and washed with water. Then, the filtrate was acidified with dilute aqueous HCl and extracted with diethyl ether (3 10 mL). The organic phases were combined, and the volatile components were evaporated under reduced pressure. Purification by flash column chromatography on silica gel (70%hexanes/ 30% ethyl acetate) afforded 0.1433 g of 3,4-dimethoxyphenol (2f) in 93% isolated yield as an off-white solid
88%
With dihydrogen peroxide; In water; at 20℃; for 0.5h;
General procedure: To a 25 mL round-bottom flask equipped with a magnetic stir bar, phenylboronic acid (3.0 mmol), PCL membrane (1.0 mg), H2O2 (aq. 30 wt%, 0.30 mL) and H2O (3.0 mL) were added. Then, the mixture was stirred at room temperature in open air for 30 min. The reaction mixture was filtered out the catalyst for reuse. The aqueous layer was acidified with 3M HCl aqueous solution and then extracted with diethyl ether (3 X 10 mL). The combined organic layers were dried with anhydrous Na2SO4, then evaporated under reduced pressure. The crude mixture was purified by column chromatography on silica gel (hexanes/ diethyl ether).
2-methyl-9,10-di(3-quinolinyl)anthracene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
85%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran;Inert atmosphere; Schlenk technique; Reflux;
General procedure: 2MADN was synthesized by the Suzuki cross-coupling reaction. A two-necked flask containing the compound MADBr (1.00g, 2.85mmol), 2NB (1.70g, 9.99mmol), tetrakis(triphenylphosphine)palladium(0) (300mg, 2.60mmol), and 2M K2CO3 (3mL) and THF (40mL) was equipped with a magnetic stirrer and a reflux condenser was heated to reflux overnight under a N2 purge. The mixture was then poured into water and extracted with 50mL dichloromethane (DCM). The combined organic layer was dried with anhydrous MgSO4 and evaporated to dryness. The crude product was purified by silica-gel column chromatography using hexane as eluent affording the title compound as a pale yellow solid (80% yield).
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In N,N-dimethyl-formamide; at 120℃; for 16h;
Step A: 5-(quinolin-3-yl)thiazole To a solution of <strong>[3034-55-7]<strong>[3034-55-7]5-bromothiazol</strong>e</strong> (3 g, 18.29 mmol), quinolin-3-ylboronic acid (4.75 g, 27.4 mmol), Pd(Ph3P)4 (2.114 g, 1.829 mmol) and K2C03 (7.58 g, 54.9 mmol) in DMF (50 mL) was heated to 120 C and stirred for 16 h. TLC (petroleum ether: EtOAc=5: 1) showed that the reaction was complete. To the resulting mixture was added a.q NaCl (100 mL) and extracted with DCM (100 mL*3). The organic layers were concentrated in vacuo to give crude which was purified by silica gel column chromatography (EtOAc in petroleum ether: 0-15%) to give 5- (quinolin-3-yl)thiazole as a solid. XH NMR (CDC13, 400 MHz): delta 9.17 (d, J= 2.0 Hz, 1H), 8.89 (s, 1H), 8.31 (d, J= 2.0 Hz, 1H), 8.28 (s, 1H), 8.14 (d, J= 8.8 Hz, 1H), 7.88 (d, J= 8.0 Hz, 1H), 7.76 (td, J= 0.8 Hz, 8.0 Hz, 1H), 7.47 (td, J= 2.4 Hz, 8.0 Hz, 1H).
With oxygen; In 1-methyl-pyrrolidin-2-one; at 20.0℃; for 1.0h;
General procedure: Arylboronic acid 2 (0.12 mmol) and (bpy)Cu(SCF3) 1 (0.1 mmol) were added to a Schlenk flask fitted with magnetic stir bar and O2 balloon. The flask was evacuated and back filled with O2. The solvent NMP (2.0 mL) was added by syringe at room temperature and the solution was stirred for 1 h. For the products reported with isolated yields (3a, 3k, 3l, 3m, 3n, 3o, 3p, 3q, 3r, 3s, 3t, 3u and 3w), the reaction mixture was diluted with EtOAc, then washed with water and brine. The organic phase was dried over anhydrous Na2SO4 and filtered. The filtrate was concentrated under reduced pressure and the residue was purified by flash chromatography on silica gel (n-hexane/ethyl acetate gradient) to afford the desired compounds. Gram-scale synthesis of compound 5 was prepared following the similar procedure. The relatively volatile products (3b, 3c, 3d, 3e, 3f, 3g, 3h, 3i, 3j and 3v) were not isolated and their yields were determined by 19F NMR measurement in CDCl3 of the reaction mixture. For the products reported with 19F NMR yields, PhOCF3 (1.0 equiv) was added to the reaction mixture as internal standard added after the reaction completed. The reaction mixture was purified by flash chromatography on silica gel (pentane/diethyl ether gradient) to afford the desired compounds.
With potassium phosphate; 4,4'-Dimethoxy-2,2'-bipyridin; nickel dibromide; In diethylene glycol dimethyl ether; at 80℃; for 24h;Inert atmosphere; Sealed tube;
In a nitrogen atmosphere, 3-quinolineboronic acid (2.595 g, 15.0 mmol) was added sequentially to the tube.Potassium phosphate anhydrous(6.368g, 30.0mmol),After adding solvent diethylene glycol dimethyl ether (60mL) and stirring,Then add <strong>[762-51-6]1-fluoro-2-iodoethane</strong> in turn(1.739g, 10.0mmol),4,4'-dimethoxy-2,2'-dipyridyl(0.119g, 0.55mmol)And NiBr2 (0.110 g, 0.50 mmol),After sealing, the reaction is stirred for 24 hours in an oil bath at 80C.Cool the reaction solution to room temperatureThe insoluble matter in the reaction solution was filtered off with a celite sand core funnel.A small amount of ether was rinsed and the filtrate was collected.Add 60mL of water, ether to the filtrateExtract the aqueous phase (40mL x 3) and combine the organic phases,The organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate.Filtration, recovery of solvent by rotary evaporation, separation of the residue by silica gel column chromatography,The product 1.348 g was obtained with a yield of 79%.
7-(quinolin-3-yl)-[1,2,4]triazolo[1,5-a]pyridin-2-amine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
52%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; at 150℃; for 0.5h;Microwave irradiation;
General procedure: To a microwave tube was added [1,2,4]triazolo[1,5-a]pyridin-2-amine 13 (1 equiv), K2CO3 (2.0 equiv), Pd(PPh3)4 (0.056 equiv), and the corresponding boronic acid (1.5 equiv). 5 mL of EtOH:H2O (1:1) was used as solvent, and the microwave conditions employed were 150 C for 30 min. After solvent evaporation, the product was purified by flash chromatography on silica gel using as eluent a gradient of EtOAC (0 - 100%) in n-hexane or MeOH (0 - 10%) in DCM to afford the desired compound 16 (adapted from 4).
General procedure: A mixture of compound 4 (104.6 mg, 0.200 mmol), pyridine-3-boronic acid (52.1 mg, 0.424 mmol), Pd2(dba)3 (6.7 mg, 0.007 mmol), K3PO4 (198.2 mg, 0.934 mmol), H2O (0.5 mL), dioxane (0.5 mL), and 0.6 M tricyclohexylphosphine (20 muL,0.012 mmol) was refluxed under an argon atmosphere for 15 h. The reaction mixture was filtered, washed with EtOAc, and concentrated in vacuo. The residue was purified by column chromatography over silica gel (n-hexane-EtOAc) to give amixture of regioisomers 5a (40.2 mg, 43%) as a yellow oil. 1H-NMR (270 MHz, CDCl3, major peaks of regioisomers) delta: 8.86 (1H, d, J = 1.9 Hz), 8.62-8.64 (1H, m), 8.25 (1H, d,J = 5.4 Hz), 8.14 (1H, s), 7.88-7.91 (2H, m), 7.30-7.37 (2H, m), 7.10 (1H, s), 6.79-6.83 (2H, m), 6.56 (1H, d, J = 5.4 Hz), 5.51(2H, s), 3.80 (3H, s), 3.67-3.80 (2H, s), 0.91-1.01 (2H, m), 0.01 (9H, s). LC/MS (ESI): m/z 475 [M + H]+.
N-(4-methoxyphenyl)-4-(3-quinolin-3-yl-1H-pyrazol-4-yl)pyrimidin-2-amine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
General procedure: To a solution of compound 5a (40 mg, 0.084 mmol) in dry THF (6 mL) was added 1 M TBAF in THF (0.17 muL). The reaction mixture was refluxed for 3.5 h and added to brine, extracted with EtOAc, dried over Na2SO4, filtered, and concentrated in vacuo. The residue was purified by column chromatography over silica gel (CH2Cl2-MeOH) to afford compound 6a (23.3 mg, 81%) as a yellow solid.
With tetrakis(triphenylphosphine) palladium(0); caesium carbonate In tetrahydrofuran; water at 65℃; for 4.5h; Inert atmosphere;
4.3. General synthetic procedures for arylnaphthoquinones 3a-r
General procedure: Under exclusion of air or humidity, bromonaphthoquinone 2(237 mg, 1 mmol) and Cs2CO3 (489 mg, 1.5 mmol) were addedsuccessively to a stirred solution of Pd(PPh3)4 (29 mg, 0.025 mmol)in anhydrous THF (4 mL). Then, 0.6 mL of H2O and 1.5 mmol of thecorresponding boronic acid were added and the reaction mixturewas heated to 65 C until TLC showed complete consumption of thestarting material (1.5e20 h). After cooling to ambient temperature,the mixture was diluted with water (15 mL) and extracted severaltimes with EtOAc. The combined organic layers were dried overNa2SO4 and concentrated in vacuo to give a residue, which waspurified by flash chromatography.
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