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CAS No. : | 40263-57-8 | MDL No. : | MFCD00023421 |
Formula : | C5H4INO | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | HJBGMPCMSWJZNH-UHFFFAOYSA-N |
M.W : | 221.00 | Pubchem ID : | 97179 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | |
Hazard Statements: | H315-H319-H335 | Packing Group: | |
GHS Pictogram: |
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* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In tetrahydrofuran; at 70℃; for 14h;Inert atmosphere; | A mixture of <strong>[40263-57-8]2-iodo-3-hydroxypyridine</strong> (1 g, 4.5 mmol, 1.0 eq), 3,3-diethoxyprop-1-yne (754.0 mg, 5.9 mmol,1.3 eq), TEA (4.1 g, 41 mmol, 9.0 eq), CuT (172 mg, 905 imol, 0.2 eq) and Pd(PPh3)2C12 (318mg, 453 imol, 0.1 eq) in 10 mL of THF was degassed and purged with N2 three times. The mixture was stirred at 70 C for 14 hours under N2 atmosphere. The reaction mixture was concentrated in vacuo. The residue was purified by column chromatography (Si02, eluting with petroleum ether: ethyl acetate = 100:1 to 2:1) to afford 820 mg of 2-(diethoxymethyl)furo[3,2- bjpyridine (3.7 mmol, 82% yield) as yellow oil. |
With copper(l) iodide; triethylamine;bis-triphenylphosphine-palladium(II) chloride; In N,N-dimethyl-formamide; for 17h; | 2-Iodo-3-pyridinol (24 mmol), triethylamine (1.0 eq), 3,3-diethoxy-1-propyne (1.0 eq), bis(triphenylphosphine)palladium (II) chloride (0.02 eq), and copper(I) iodide (0.04 eq) were combined in DMF (14 mL) and allowed to stir for 17 hours. The mixture was diluted with ethyl acetate (100 mL) and filtered through a Celite pad. The filtrate was washed with saturated sodium bicarbonate (2*50 mls), dried over anhydrous magnesium sulfate, filtered, and the filtrate concentrated under reduced pressure to provide the title compound which was used in the next step without further purification. 1H NMR (CDCl3, 400 MHz) δ 1.28 (t, J=7.1 Hz, 6H), 3.70 (q, J=7.1 Hz, 4H), 5.68 (s, 1H), 7.05 (s, 1H), 7.23 (dd, J=8.5, 4.8 Hz, 1H), 7.77 (d, J=8.5 Hz, 1H), 8.57 (br, 1H). MS (DCI/NH3) m/z 222 (M+H)+. | |
With copper(l) iodide;bis-triphenylphosphine-palladium(II) chloride; for 17h; | [2-IODO-3-PYRIDINOL] (24 mmol), triethylamine (1.0 [EQ),] 3, [3-DIETHOXY-1-PROPYNE] (1.0 eq), bis (triphenylphosphine) palladium [(II)] chloride (0.02 [EQ),] and copper [(I)] iodide (0.04 eq) were combined in DMF (14 mL) and allowed to stir for 17 hours. The mixture was diluted with ethyl acetate (100 mL) and filtered through a Celite pad. The filtrate was washed with saturated sodium bicarbonate (2x50mls), dried over anhydrous magnesium sulfate, filtered, and the filtrate concentrated under reduced pressure to provide the title compound which was used in the next step without further [PURIFICATION.'H] NMR [(CDC13,] [400MHZ)] [5] 1.28 (t, J=7. [1HZ,] 6H), 3.70 (q, J=7. [1HZ,] 4H), 5.68 (s, 1H), 7.05 (s, [1H),] 7.23 (dd, J=8.5, 4.8Hz, [1H),] 7.77 (d, J=8. 5Hz, 1H), 8.57 (br, 1H). MS (DCI/NH3) [M/Z] 222 (M+H) [+.] |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
6 g | To a stirred solution of <strong>[40263-57-8]3-hydroxy-2-iodopyridine</strong> (10 g, 45.24 mmol) in THF : DMF (10 mL: 20 mL) at 0 C was added tert-BuO-K (6 g, 54.3 mmol) portion wise. After stirring the reaction mixture for 30 mi methoxymethyl chloride (4 mL, 50 mmol) was added at 0 C and the resulting mixture was allowed to stir at room temperature for 3 hrs. Reaction mixture was diluted with brine and extracted with EtOAc (3 x 150 mL). EtOAc part was dried over anhydrous sodium sulfate, concentrated under reduced pressure to afford crude mass which was purified by column chromatography using silica (100-200 mesh) and EtOAc-hexane as eluent to afford 2-iodo-3- (methoxymethoxy)pyridine (6.0 g) as off white solid. | |
9.9 g | To a solution of <strong>[40263-57-8]2-iodo-3-hydroxypyridine</strong> (CAS No. 40263-57-8) (9.67 g, 43.8 mmol, 1 equivalent) in THF (200 mL) was added sodium hydride (60% oil dispersion, 1.93 g, 48.1 mmol, 1.1 equivalents) at 0 C., and the reaction mixture was stirred at 0 C. for 10 minutes. To the solution was added chloromethyl methyl ether (3.66 mL, 48.1 mmol, 1.1 equivalents), and the mixture was stirred at 0 C. for 10 minutes and at room temperature for 1 hour. To the reaction mixture was added water, and then the mixture was concentrated under reduced pressure. The residue was extracted with chloroform, and the organic layer was concentrated under reduced pressure. The residue was purified with silica gel column chromatography (NH silica gel, 0%-40% ethyl acetate/n-heptane) to afford the title compound (9.9 g). 1H-NMR (400 MHz, CDCl3) δ (ppm): 3.52 (s, 3H), 5.27 (s, 2H), 7.18 (dd, J=8.2, 4.5 Hz, 1H), 7.28 (dd, J=8.2, 1.6 Hz, 1H), 8.06 (dd, J=4.5, 1.6 Hz, 1H). MS [M+H]+=266 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With copper(l) iodide; L-proline; sodium hydroxide; In dimethyl sulfoxide; at 80℃; for 12h;Inert atmosphere; Sealed tube; | General procedure: A sealable reaction tube equipped with a magnetic stirrer bar was charged with 2-iodophenols 1 (1 mmol), alkynes 2 (1 mmol), NaOH (2 mmol), CuI (0.1 mmol), proline (0.3 mmol) and DMSO (5 mL), and the reaction vessel placed in an oil bath at 80 C under N2 . After stirring the mixture at this temperature for 12 h, it was cooled to room temperature and diluted with ethyl acetate, washed with water and brine, dried over by MgSO4. After the solvent was removed under reduced pressure, the residue was purified by column chromatography on silica gel to afford the corresponding product. |
79% | With potassium phosphate; In N,N-dimethyl-formamide; at 160℃;Schlenk technique; Inert atmosphere; Glovebox; Green chemistry; | General procedure: General produce: o-iodophenol (0.5 mmol), alkyne (1.0 mmol) andbase (1.0 mmol) were added into a 10 mL dry Schlenk tube under Ar,then anhydrous DMF (5 mL) was injected into the mixture using syringe.Then the solution stirred at preheated oil bath (160 C). The reactionwas monitored by TLC and GC.The mixture was cooled down toroom temperature after full conversion, then diluted with dichloromethaneand washed with water three times. The organic layerwas separated and washed with brine followed by drying with anhydrousNa2SO4. The filtrate was concentrated in vacuo to afford thecrude product, which was purified by flash column chromatography onsilica gel (petroleum ether). |
63% | With potassium phosphate; C43H36N4O4Pd; In dimethylsulfoxide-d6; at 120℃; for 10h; | General procedure: In a typical run, performed in air, a 25 mL of round bottom askwas charged with a mixture of 2-iodophenol (0.50 mmol), terminalalkyne (0.60 mmol), and K3PO4 (1.00 mmol). A palladium complex(2a or 2b, 0.0005 mmol) was added to the mixture, followed byDMSO (ca. 2 mL) as a solvent, and then the reaction mixture washeated (either at 90C or at 120C) for 10 h. The reaction mixturewas cooled to room temperature, and water (ca. 20 mL) was added.The resulting mixture was extracted with EtOAc (ca. 50 mL). Theorganic layer was further extracted with EtOAc (ca. 2 20 mL). Theorganic layers were combined and vacuum dried to obtain a crudeproduct that was subsequently puried by column chromatog-raphy. The obtained benzofuran derivatives (3aa3ap) were char-acterized by NMR and Mass spectroscopy (See SupportingInformation Figures S4-S23). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine;bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; In toluene; at 90℃; for 5h; | 6-Ethynyl-3-[4-((l S,3R,5R)-8-methyl-8-azabicyclo[3.2.1]oct-3-yloxy)phenyl]-3H-thieno[3,2- d]pyrimidin-4-one (39.2 mg), bis(triphenylphosphine)palladium chloride (3.5 mg) and copper iodide (0.95 mg) were added to a solution of 2-iodo-3-pyridinol (22.1 mg) and triethylamine (0.272 mL) in toluene (1.36 mL). The reaction mixture was heated at 900C for 5 hours. The solvent was then removed in vacuo, the residue was taken up in ethyl acetate and water, and the organic phase was acidified with 2N hydrochloric acid. The organic phase was then washed with water and saturated sodium chloride solution, dried over sodium sulfate and concentrated. The crude product was purified by preparative HPLC. The product with the molecular weight of 484.58 (C27H24N4O3S) was obtained in this way; MS (ESI): 485 (M+H+). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine;bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; at 70℃; for 16h;Under nitrogen; | Intermediate 11 Ethyl ?-^-furotS^-blpyridin^-yOpheny^-Z-I^frans-?methylcyclohexylJcarbonylKI- methylethyl)amino]-3-furancarboxylateTo Intermediate 10 (78 mg) was added <strong>[40263-57-8]2-iodo-3-hydroxypyridine</strong> (40.8 mg), bis(triphenylphosphine)palladium dichloride (13 mg), copper (I) iodide (3.5 mg) and triethylamine (1.2 mL). The reaction was stirred at 7O0C, under nitrogen, for 16 h. The reaction was cooled, partitioned between saturated sodium bicarbonate solution and DCM1, passed through a hydrophobic and then concentrated. The crude product was dissolved in DCM, filtered and purified by ISCO companion silica chromatography eluting with a gradient of ethyl acetate in cyclohexane (0% to 100%) to give the title compound. MS calcd for (C3IH34N2O5 + H)+: 515 MS found (electrospray): (M+H)+ = 515 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine;bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; at 70℃; for 17h; | Intermediate 33Ethyl 5-(4-furo[3,2-b]pyridin-2-ylphenyl)-2-[[(fra?s-4- methylcyclohexyl)carbonyl](tetrahydro-3-furanyl)amino]-3-furancarboxylateA mixture of Intermediate 32 (228 mg), <strong>[40263-57-8]2-iodo-3-hydroxypyridine</strong> (112 mg), copper(l) iodide (10 mg), dichlorobis(triphenylphosphine)palladiurr) (II) (36 mg) and triethylamine (3.5 ml_) were stirred and heated in a Reacti-vial at 700C for 17 h. The reaction was cooled, partitioned between saturated sodium bicarbonate solution and DCM, separated using a hydrophobic frit and the organics were evaporated in vacuo. The crude material was purified by ISCO Companion silica chromatography, eluting with a gradient 0-100% EtOAc in cyclohexane to give the title compound. MS calcd for (C32H34N2O6 + H)+: 543 MS found (electrospray): (M+H)+ = 543 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine;bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; at 70℃; | Intermediate 37Ethyl 5-(4-furo[3,2-b]pyridin-2-ylphenyl)-2-[(frans-4-methylcyclohexyl)carbonyl][2- (methyloxy)ethyl]amino}-3-furancarboxylateA mixture of Intermediate 36 (220 mg), 2-?odo-3-hydroxypy?d?ne (1 12 mg), copper(l) iodide (10 mg), d?chlorob?s(t?phenylphosphine)pallad?um (II) (36 mg) and triethylamine (3 5 ml_) were heated in a Reacti-vial at 7O0C overnight. The reaction was cooled to room temperature, partitioned between saturated sodium bicarbonate solution and DCM, separated using a hydrophobic frit and the organics were evaporated in vacuo The crude material was purified by ISCO Companion silica chromatography, eluting with a gradient 0- 100% EtOAc in cyclohexane to give the title compound. MS calcd for (C31H34N2O6 + H)+- 531 MS found (electrospray)- (M+H)+ = 531 |
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