* 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] Organic Letters, 2004, vol. 6, # 19, p. 3337 - 3340
[2] Journal of Organic Chemistry, 2017, vol. 82, # 1, p. 76 - 85
[3] Journal of the Chemical Society - Perkin Transactions 1, 1996, # 6, p. 515 - 518
[4] Patent: WO2005/811, 2005, A1, . Location in patent: Page/Page column 58; 123
2
[ 1692-25-7 ]
[ 6630-33-7 ]
[ 176690-44-1 ]
Yield
Reaction Conditions
Operation in experiment
64%
With sodium carbonate In water; N,N-dimethyl-formamide at 110℃; Inert atmosphere
Example 380 : Synthesis of (1E,6E)-1-(4-hydroxyphenyl)-7-[2-(pyridin-3-yl)phenyl]hepta-1,6-diene-3,5-dione (CU513); (1) Synthesis of 2-(pyridin-3-yl)benzaldehyde; To a suspension of 1-bromobenzaldehyde (250 μL, 2.14 mmol), sodium carbonate (270 mg, 2.55 mmol), and 3-pyridineboronic acid (289 mg, 2.35 mmol) in 4.2 mL of N,N-dimethylformamide/water (2:1) were added palladium acetate (24 mg, 0.11 mmol) and triphenylphosphine (115 mg, 0.44 mmol) under nitrogen. After being stirred at 110°C overnight, the reaction mixture was filtered. The filtrate was diluted with chloroform, and the solution was washed with brine, and dried over MgSO4. After filtration, the filtrate was concentrated in vacuo, and the residue was purified by silica gel column chromatography (chloroform/methanol = 99/1 to 95/5) to obtain the title compound as a white powder (250 mg, 64percent).
With potassium carbonate In ethanol; water at 120℃; for 0.166667 h; Microwave irradiation; Sealed tube
General procedure: In a 10-mL glass tube were placed halide (1.0mmol); 2-formylphenyl or 2-pyridyl MIDA boronate (1.5mmol) or allyl MIDA boronate; K2CO3 (3.0 mmol); Pd EnCat30(6molpercent); and ethanol/H2O (4:1v/v) or water, and a magnetic stir bar. The vessel was sealed with a septum and placed into the microwave cavity. The temperature was ramped from rt to 120°C or 135°C. Once the reaction temperature was reached, the reaction mixture was held at this temperature for 10–18 min. After the mixture was allowed to cool to room temperature, the reaction vessel was opened and the contents were poured into a separating funnel. Water and ethylacetate (3×10mL) were added. The combined organics were dried over Na2SO4, filtered, and concentrated in vacuo. The organic residue was adsorbed onto silicagel, and then purified by column flash chromatography (hexane = ethyl acetate as eluent) to afford the desired product 1a–x. The biaryls, bipyridines, or allylphenols prepared are known compounds. [23–45] The products were confirmed by comparing the 1H NMR and mass spectral data with authentic samples reported in the literature.
Reference：
[1] European Journal of Organic Chemistry, 2012, # 31, p. 6248 - 6259,12
[2] European Journal of Organic Chemistry, 2012, # 31, p. 6248 - 6259
With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In acetonitrile; at 60℃; for 72h;
To Pd (PPh3) 4 (0.085g, 0. 07mmol) in acetonitrile (6mL), under nitrogen, was added water (2mL) followed by 2-formylphenylboronic acid (0. 55g, 3. 68mmol), 3-bromopyridine (0.36 mL, 3.68mmol) and potassium carbonate (2.69g, 22. 07mmol). After stirring for 3 days at 60C, the reaction mixture was purified by flash chromatography on silica, eluting with ethyl ACETATE/ISOHEXANE (10: 90 to 30: 70), to give the title compound as an oil. MS: [M+H] = 184.
1,1-dimethylethyl (3S)-3-((2-methylpropyl)[2-(3-pyridyl)phenyl]methyl}amino)pyrrolidine-1-carboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With sodium tris(acetoxy)borohydride; In 1,2-dichloro-ethane; at 20℃; for 24h;
Sodium triacetoxyborohydride (0.35g, 1.64mmol) in DMF (IML) was added to a stirred solution of 1, 1-dimethylethyl (3S)-3-(2-METHYLPROPYLAMINO) PYRROLIDINE-1-CARBOXYLATE and 2- (3-pyridyl) benzaldehyde (0.265g, 1. 09mmol) in 1,2-dichloroethane (4mL). After stirring under nitrogen at room temperature for 1 day, the reaction mixture was purified by flash chromatography on silica, eluting with ethyl acetate/isohexane (0: 100 to 40: 60), to give the title compound as an oil. MS: [M+H] = 410
With sodium tetrahydroborate; In methanol; at 0℃; for 1.5h;Heating / reflux;
To a solution of <strong>[176690-44-1]2-pyridin-3-yl-benzaldehyde</strong> (1 g, 5.46 mmole) in methanol (10 ml) was added a solution of NaBH4 (0.26 g, 6.82 mmole) in methanol (10 ml) at 0 C and stirred for 30 min at same temperature and then refluxed for 1 h. The unreacted NaBH4 was decomposed by solution of 6N HCI. The solvent was removed under reduced pressure and the residue was dissolved in 5N NaOH (20 ml) and extracted with ethyl acetate (3X20 ml). Combined organic extracts were dried (Na2S04), filtered and concentrated to yield 0.95 g (94%) of product. MS (ESI+) m/z 186 (M+H) +.
(a) 2-Pyrid-3-ylbenzaldehyde: In a similar manner to that of Example 21(a), starting with 2.50 g (16.7 mmol) of 2-formalbenzeneboronic acid and 1.76 g (11.1 mmol) of 3-bromopyridine, 1.48 g (73%) of the expected compound are obtained in the form of a yellow powder with a melting point of 54 C. 1 H NMR (CDCl3) delta 7.40 to 7.45 (m, 2H), 7.58 (t, 1H, J=7.5 Hz), 7.69 (dd, 1H, J=7.4/1.5 Hz), 7.72 (dd, 1H, J=7.9/2.0 Hz), 8.07 (dd, 1H, J=7.8/1,3 Hz), 8.67 to 8.72 (m, 2H), 9.99 (s, 1H).
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; for 5h;Inert atmosphere; Reflux;
General procedure: Ethanol (500 mE), boronic acid Ar2-B(OH)2 (92.7 mmol, 1.2 eq) and bromoarylaldehyde or bromoheteroarylaldehyde Br-Ar,--CHO (77.3 mmol) are introduced in succession into a 1 E flask under argon and at ambient temperature. The solution is degassed with argon for 15 minutes. Pd(PPh3)4 (1.78 g, 1.55 mmol) and Na2CO3 (92.7 mE of a 2M solution in H20, 185 mmol, 2.4 eq) are then introduced in a single portion. Afier the addition, the reaction mixture is heated at reflux for 5 hours. The mixture is then evaporated to dryness. The residue is taken up in DCM (1 E) and H20 (200 mE). After decantation, the aqueous phase is extracted with DCM (200 mE). The organic phases are combined and then washed with a saturated NaC1 solution (400 mE), dried over Mg504 and concentrated under reduced pressure. The residue is then purified by flash chromatography on silica gel. The expected product is obtained with yields of from 59 to 94%.
19
[ 176690-44-1 ]
[ 216443-83-3 ]
Yield
Reaction Conditions
Operation in experiment
(b) 3-[2-((E)-2-Iodovinyl)phenyl]pyridine: In a similar manner to that of Example 1(d), starting with 1.48 g (8.1 mmol) of <strong>[176690-44-1]2-pyrid-3-ylbenzaldehyde</strong> obtained in Example 51(a), 600 mg (24%) of the expected compound are obtained in the form of a yellow oil. 1 H NMR (CDCl3) delta 6.82 (d, 1H, J=14.8 Hz), 7.26 to 7.30 (m, 2H), 7.34 to 7.42 (m, 3H), 7.50 to 7.53 (m, 1H), 7.63 to 7.67 (m, 1H), 8.61 to 8.65 (m, 2H).
With sodium carbonate;palladium diacetate; triphenylphosphine; In water; N,N-dimethyl-formamide; at 110℃;Inert atmosphere;
Example 380 : Synthesis of (1E,6E)-1-(4-hydroxyphenyl)-7-[2-(pyridin-3-yl)phenyl]hepta-1,6-diene-3,5-dione (CU513); (1) Synthesis of 2-(pyridin-3-yl)benzaldehyde; To a suspension of 1-bromobenzaldehyde (250 muL, 2.14 mmol), sodium carbonate (270 mg, 2.55 mmol), and 3-pyridineboronic acid (289 mg, 2.35 mmol) in 4.2 mL of N,N-dimethylformamide/water (2:1) were added palladium acetate (24 mg, 0.11 mmol) and triphenylphosphine (115 mg, 0.44 mmol) under nitrogen. After being stirred at 110C overnight, the reaction mixture was filtered. The filtrate was diluted with chloroform, and the solution was washed with brine, and dried over MgSO4. After filtration, the filtrate was concentrated in vacuo, and the residue was purified by silica gel column chromatography (chloroform/methanol = 99/1 to 95/5) to obtain the title compound as a white powder (250 mg, 64%).
General procedure: To a mixture of benzaldehyde (20.1 mg, 0.2 mmol) and isopentyl amine (16 mg, 0.2 mmol) in 500 muL of DMF was added mercaptosuccinic acid (45 mg, 0.3 mmol) and the mixture was heated at 80 C for 16 h. The reaction mixture was cooled and partitioned between ethyl acetate and water. The organics were separated and dried and solvent removed to give the thiazoldinone acetic acid. The acid (31 mg,0.1 mmol) was coupled with 3-(piperidin-4-yl)-3,4-dihydroquinazolin-2(1H)-one (23 mg, 0.1 mmol) using HATU (38 mg, 0.1 mmol) in the presence of diisopropyl ethyl amine (44 muL, 0.25 mmol) in 300 muL of DMF at ambient temperature, and was purified with 10-90% acetonitrile/water to give 3-isopentyl-5-(2-oxo-2-(4-(2-oxo-1,2-dihydroquinazolin-3(4H)-yl)piperidin-1-yl)ethyl)-2-phenylthiazolidin-4-one as the desired product.
2-formylphenylboronic acid N-methyliminodiacetic acid ester[ No CAS ]
[ 176690-44-1 ]
Yield
Reaction Conditions
Operation in experiment
95%
With potassium carbonate; In ethanol; water; at 120℃; for 0.166667h;Microwave irradiation; Sealed tube;
General procedure: In a 10-mL glass tube were placed halide (1.0mmol); 2-formylphenyl or 2-pyridyl MIDA boronate (1.5mmol) or allyl MIDA boronate; K2CO3 (3.0 mmol); Pd EnCat30(6mol%); and ethanol/H2O (4:1v/v) or water, and a magnetic stir bar. The vessel was sealed with a septum and placed into the microwave cavity. The temperature was ramped from rt to 120C or 135C. Once the reaction temperature was reached, the reaction mixture was held at this temperature for 10-18 min. After the mixture was allowed to cool to room temperature, the reaction vessel was opened and the contents were poured into a separating funnel. Water and ethylacetate (3×10mL) were added. The combined organics were dried over Na2SO4, filtered, and concentrated in vacuo. The organic residue was adsorbed onto silicagel, and then purified by column flash chromatography (hexane = ethyl acetate as eluent) to afford the desired product 1a-x. The biaryls, bipyridines, or allylphenols prepared are known compounds. [23-45] The products were confirmed by comparing the 1H NMR and mass spectral data with authentic samples reported in the literature.
methyl (Z)-3-(2-(pyridin-3-yl)phenyl)acrylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
64%
Stage #1: Bis(2,2,2-trifluoroethyl)(methoxycarbonylmethyl)phosphonate With 18-crown-6 ether; 1,1,1,3,3,3-hexamethyldisilazane potassium In tetrahydrofuran at -78℃; for 0.25h;
Stage #2: 2-(pyridin-3-yl)benzaldehyde In tetrahydrofuran at 2℃; for 0.5h;
(E)-N-methoxy-N-methyl-3-(2-(pyridin-3-yl)phenyl)acrylamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
92%
Stage #1: diethyl (2-(methoxy(methyl)amino)-2-oxoethyl)phosphonate With sodium hydride In tetrahydrofuran at 0℃; for 0.25h;
Stage #2: 2-(pyridin-3-yl)benzaldehyde In tetrahydrofuran at 50℃;
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