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CAS No. : | 1151802-22-0 | MDL No. : | MFCD16659007 |
Formula : | C12H19BN2O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | NLWYVKHISUTBMY-UHFFFAOYSA-N |
M.W : | 234.10 | Pubchem ID : | 59327133 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* 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 |
---|---|---|
With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; at 110℃; for 0.166667h; | Example 6; Synthesis of 2-(3-chloro-5-( 1 -cyclopropyl- 1 H-pyrazol-4-yl)phenyl)-N-(4-(2-methylpyridin-4- yl)phenyl)propanamideA clear microwave vial was charged with 2-(3-bromo-5-chlorophenyl)-N-(4-(2- methylpyridin-4-yl)phenyl)propanamide (0.150 g, 0.349 mmol), l-cyclopropyl-4-(4,4,5,5- tetramethyl-l,3,2-dioxaborolan-2-yl)-lH-pyrazole (0.0981 g, 0.419 mmol), tetrakis(triphenylphosphine)palladium (0.0202 g, 0.0175 mmol), sodium carbonate (0.349 ml, 0.698 mmol) and dioxane (4 mL). The vial was flushed with nitrogen and capped. The vial was heated in a Personal Chemistry SmithSynthesizer to 1100C for 10 minutes. The reaction mixture was diluted with ethyl acetate and water. The organic portion was washed with an aqueous saturated solution of sodium bicarbonate, then with water and then brine. The organic layer was then dried with sodium sulfate, reduced and purified by RP-HPLC using a gradient of 5percentACN 0.1percent TFA to 95percent ACN 0.1percent TFA in water 0.1percent TFA. The pure fractions were neutralized with ammonium hydroxide and the volatiles were removed under reduced pressure. The solid that crashed out of the aqueous layer was filtered off, washed with water and dried in <n="112"/>a vacuum oven at 45 degrees to give 2-(3-chloro-5-(l-cyclopropyl-lH-pyrazol-4-yl)phenyl)-N- (4-(2-methylpyridin-4-yl)phenyl)propanamide as an off-white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium acetate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In N,N-dimethyl-formamide; at 150℃; for 1h;Inert atmosphere; Sealed microwave vial; | Bis(pinacolato)diboron (330 mg, 1.3 mmol), NaOAc (262 mg, 3.2 mmol), and Pd(dppf)Cl2-dichloromethane complex (89 mg, O. l lmmol) were combined in a microwave vial. 4-Bromo-l -cyclopropyl- lH-pyrazole and DMF (4 mL) were added and the vial was flushed with argon and sealed. The reaction mixture was heated in a microwave for 60 min at 150 0C. The reaction was diluted with 10 mL water and extracted 3 x 10 mL with EtOAc. The combined organic layers were dried over Na2Spsi4 and concentrated to yield 120 mg of the title compound as a dark oil, m/z 235.4 [M +H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | Step 2In a flask 1-cyclopropyl-4-iodo-1H-pyrazole (405 mg, 1.73 mmol) was dissolved in THF (8.0 mL) and the solution cooled to 0° C.Isopropylmagnesium chloride (2.0 M in THF, 1.04 mL, 2.08 mmol) was added dropwise and the mixture stirred at 0° C. for 45 min, after which 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.53 mL, 2.60 mmol) was added and the mixture allowed to warm to room temperature over 1 h.The mixture was quenched with 50percent sat aqueous NH4Cl and extracted with EtOAc.The organic extract was washed with sat.NaCl, dried over MgSO4 and the solution was concentrated.The residue was purified by SiO2 chromatography (20-50percent EtOAc/heptane) to afford 405 mg (83percent) of 1-cyclopropyl-1H-pyrazole-4-boronic acid pinacol ester as a colorless viscous oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Step 1 : l-Cyclopropyl-4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-lH-pyridaziiie To a 100 n L flask is added 4-bromo-l-cyclopropylpyrazol (6.57 g, 35.1 mmol) and anhydrous THF (30 niL). The solution is cooled to -78 °C under nitrogen; then n-butyl lithium (15.5 n L, 2.5 M in hexanes, 38.6 mmol) is added dropwise. The reaction mixture is stirred at the temperature for 1 hr, followed by addition of isopropyl boronate (9.17 g, 94.1 mmol) and stirred below -70 °C for 3 hours. The reaction is quenched with water (20 n L) and the resulted mixture is adjusted to pH 8-9 with aqueous hydrochloride solution (1 N). The combined organic phases are concentrated and used in next step without further purification (6.64 g, 81percent yield). (MS: [M+l] 235) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
407 g | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium phosphate; In 1,4-dioxane; water; at 20 - 90℃;Inert atmosphere; | 3-Chloro-6-(l-cyclopropy -lH-pyrazol-4-yl)pyridazine To a 100 mL round bottom flask is added the above solid (6.64 g, 28.4 mol), 3,6-dichoropyridazine (8.46 g, 56.8 mmol), Pd(dppf)Cl2 (1.04 g, 1.42 mol) potassium phosphate (18.1 g, 85.2 mmol), water (5 mL), and 1,4-dioxane (50 g) at room temperature under nitrogen. The reaction mixture is stirred at 90 °C overnight. After cooled to 30 °C, water (20 mL) is added. The aqueous phase is isolated and extracted with ethyl acetate (3 X 30 mL). The combined organic phases are concentrated and the residue is purified on a silica gel flash chromatography to provide a yellow solid (4.07 g, 65percent yield). (MS: [M+l] 222) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Example 235 N-(5-((2S,5R,6S)-5-amino-6-fluorooxepan-2-yl)-1-methyl-1H-pyrazol-4-yl)-2-(1-cyclopropyl-1H-pyrazol-4-yl)thiazole-4-carboxamide 235 Following the procedure for Example 101 starting from tert-butyl ((3S,4R,7S)-7-(4-(2-bromothiazole-4-carboxamido)-1-methyl-1H-pyrazol-5-yl)-3-fluorooxepan-4-yl)carbamate (Intermediate 99), and replacing 3,6-dihydro-2H-pyran-4-boronic acid pinacol ester with <strong>[1151802-22-0]1-<strong>[1151802-22-0]cyclopropyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole</strong></strong> gave 235. 1H NMR (400 MHz, DMSO-d6) delta 9.75 (s, 1H), 8.44 (s, 1H), 8.22 (s, 1H), 8.03 (s, 1H), 7.90 (s, 1H), 4.92-4.83 (m, 1H), 4.59-4.40 (m, 1H), 4.32 (dd, J=22.2, 15.0 Hz, 1H), 4.19-3.93 (m, 1H), 3.80 (dd, J=7.4, 3.7 Hz, 1H), 3.77 (s, 3H), 3.38-3.31 (m, 1H), 2.12-2.03 (m, 1H), 1.87-1.66 (m, 5H), 1.17-0.96 (m, 4H). LCMS (ES+) m/z 446 (M+1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With chloro(2-dicyclohexylphosphino-2?,4?,6?-triisopropyl-1,1?-biphenyl)[2-(2?-amino-1,1?-biphenyl?)]palladium(II); caesium carbonate; In 1,4-dioxane; water; at 100℃; for 2h; | Step 2. (S)-l-(6-(l-cyclopropyl-lH-pyrazol-4-yl)-2-methyl-5-(quinazolin-2-yloxy)-3,4- dihydroquinolin-l(2H)-yl)ethanone [0344] A mixture of (S)-l-(6-bromo-2-methyl-5-(quinazolin-2-yloxy)-3,4-dihydroquinolin-l(2H)- yl)ethanone (0.025 g, 0.061 mmol), l-cyclopropyl-4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)- lH-pyrazole (0.017 g, 0.073 mmol), chloro(2-dicyclohexylphosphino-2',4',6'-tri-i-propyl-l, - biphenyl)(2'-amino-l,r-biphenyl-2-yl) palladium(II) (XPhos 2nd generation precatalyst) (2.4 mg, 0.003 mmol), and cesium carbonate (0.059 g, 0.182 mmol) in 1 ,4-dioxane (2.0 mL) and water (0.40 mL) was heated at 100 °C for 2 h. The reaction mixture was filtered through Celite and concentrated to afford an orange oil. This material was purified via column chromatography on silica gel (Biotage 25 g column, gradient elution with 25-100percent ethyl acetate-hexane) to afford (S)-l-(6-(l- cyclopropyl- 1 H-pyrazol-4-yl)-2-methyl-5-(quinazolin-2-yloxy)-3,4-dihydroquinolin- 1 (2H)- yl)ethanone (0.012 g, 45percent) as a white solid. MS (ESI, pos. ion) m/z 440. 1H NMR (300 MHz, DMSO-i/e) delta ppm 0.81 - 0.91 (m, 5 H), 1.07 (d, J=6.74 Hz, 3 H), 1.47 (m, 1 H), 2.03 (br dd, J=13.34, 6.89 Hz, 1 H), 2.18 (s, 3 H), 2.44 (m, 1 H), 3.55 - 3.67 (m, 1 H), 4.63 (m, 1 H), 7.41 (br s, 1 H), 7.51 - 7.70 (m, 3 H), 7.72 (s, 1 H), 7.91 (ddd, J=8.50, 7.04, 1.47 Hz, 1 H), 8.06 (s, 1 H), 8.10 (d, J=8.21 Hz, 1 H), 9.54 (s, 1 H). MS (ESI, pos. ion) m/z 440 [M+H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
19% | With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium carbonate; In 1,4-dioxane; water; 1,2-dichloro-ethane; at 80℃;Inert atmosphere; | Step 2. (S)-l-(5-cyclopropoxy-6-(l-cyclopropyl-lH-pyrazol-4-yl)-2-methyl-3,4- dihydroquinolin-l(2H)-yl)ethanone. [0392] A 1.5 mL reaction vial was charged with (S)-l-(6-bromo-5-cyclopropoxy-2-methyl-3,4- dihydroquinolin-l(2H)-yl)ethanone (0.019 g, 0.06 mmol) and 1 ,4-dioxane (50 \iL). 1 -cyclopropyl- 4-(4,4,5,5-tetramethyl-l ,3,2-dioxaborolan-2-yl)-lH-pyrazole (0.2 M solution in 1 ,4-dioxane, 540 \iL, 0.108 mmol) and potassium carbonate (1 M solution in water, 180 \iL, 0.18 mmol) were added, and the reaction mixture was purged with nitrogen. [1 ,1'- Bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane adduct (0.02 M solution in 1,2-dichloroethane, 300 \iL, 0.006 mmol) was added, and the reaction was purged with nitrogen and heated to 80 °C on a heater shaker overnight. The reaction was diluted with ethyl acetate and washed with 1 N aqueous sodium hydroxide solution. The aqueous layer was separated and washed with ethyl acetate, and the combined organic layers were concentrated under a stream of nitrogen. The crude product was purified by mass triggered preparatory HPLC. The product-containing fractions were combined and concentrated in a Genevac to afford (S)-l-(5-cyclopropoxy-6-(l- cyclopropyl-lH-pyrazol-4-yl)-2-methyl-3,4-dihydroquinolin-l(2H)-yl)ethanone (0.0039 g, 19percent). MS (ESI, pos. ion) m/z 352 [M+H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium carbonate; In 1,4-dioxane; water; at 100℃; | Step 2. (S)-4-(l-acetyl-6-(l-cyclopropyl-lH-pyrazol-4-yl)-2-methyl-l,2,3,4-tetrahydroquinolin- 5-yloxy)benzamide [0496] A 50-mL, round-bottom flask was charged with (S)-4-(l-acetyl-6-bromo-2-methyl-l,2,3,4- tetrahydroquinolin-5-yloxy)benzamide (0.068 g, 0.17 mmol), l-cyclopropyl-4-(4,4,5,5-tetramethyl- l,3,2-dioxaborolan-2-yl)-lH-pyrazole (0.059 g, 0.25 mmol), [1,1'- bis(diphenylphosphino)ferrocene]dichloropalladium(II), complex with dichloromethane (0.014 g, 0.02 mmol), potassium carbonate (0.070 g, 0.50 mmol), 1 ,4-dioxane (20 mL) and water (2 mL). The resulting mixture stirred overnight at 100 °C. After cooling to room temperature, the reaction mixture was passed through a short pad of celite, and the filtrate was concentrated under vacuum. The residue was purified by preparative thin layer chromatography (eluting with 1 : 1 , ethyl acetate/petroleum ether). The product was further purified by preparative-HPLC with the following conditions (Waters I): Column, XBridge Prep CI 8 OBD Column, 19x150mm 5um 13nm; mobile phase, water (0.05percent ammonium bicarbonate) and acetonitrile (15.0percent to 95percent acetonitrile in 12 min; flow rate: 20 mL/min); Detector, UV 254/220nm. This afforded (S)-4-(l-acetyl-6-(l-cyclopropyl- lH-pyrazol-4-yl)-2-methyl-l,2,3,4-tetrahydroquinolin-5-yloxy)benzamide (0.029 g, 40percent) as an off- white solid. 1H NMR(300 MHz, CD3OD) delta ppm 0.93-1.03 (m, 4 H), 1.15 (d, J=6.60 Hz, 3 H, 1.19- 1.42 (m, 1 H), 2.18-2.27 (m, 5 H), 2.67-2.75 (m, 1 H), 3.56-3.63 (m, 1 H), 4.77-4.79 (m, 1 H), 6.85- 6.88 (m, 2 H), 7.37 (m, 1 H), 7.63 (d, J=8.40 Hz, 1 H), 7.77 (s, 1 H), 7.81-7.85 (m, 2 H), 7.94 (s, 1 H). MS (ESI, pos. ion) m/z 431 [M+H]+. |
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