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CAS No. : | 1076-96-6 | MDL No. : | MFCD00017218 |
Formula : | C10H10O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | NUMHUJZXKZKUBN-UHFFFAOYSA-N |
M.W : | 162.19 | Pubchem ID : | 583124 |
Synonyms : |
|
Num. heavy atoms : | 12 |
Num. arom. heavy atoms : | 6 |
Fraction Csp3 : | 0.1 |
Num. rotatable bonds : | 3 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 47.81 |
TPSA : | 26.3 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -5.08 cm/s |
Log Po/w (iLOGP) : | 2.37 |
Log Po/w (XLOGP3) : | 3.11 |
Log Po/w (WLOGP) : | 2.01 |
Log Po/w (MLOGP) : | 2.47 |
Log Po/w (SILICOS-IT) : | 2.5 |
Consensus Log Po/w : | 2.49 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -2.98 |
Solubility : | 0.171 mg/ml ; 0.00105 mol/l |
Class : | Soluble |
Log S (Ali) : | -3.33 |
Solubility : | 0.0757 mg/ml ; 0.000467 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -2.91 |
Solubility : | 0.2 mg/ml ; 0.00123 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.49 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | 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 |
---|---|---|
90% | With bromobenzene; at 55 - 60℃; under 3750.38 - 4500.45 Torr; for 6h;Autoclave; | General procedure: benzoic acid (Table 3, entry 1) (1.0 g,0.0081 mol), bromobenzene (0.125 g, 0.0081 mol), 10% palladium on carbon(50% wet) (0.2 g) and methanol (3 mL) were placed in autoclave vessel. Autoclave was pressurized with 1-2 bar of nitrogen followed by 1-2 bar of hydrogen gas and then put under the desired pressure of hydrogen (5-6 bar).The reaction mixtures are then warmed to 55-60 C temperature and stirredfor 4 h at 300 rpm. After reaction, the catalyst was filtered through celite bed.Filtrate was added with water (30 mL). The reaction mixture was extracted with isopropyl acetate (2 15 mL). The combined organic layers were washedwith 5% aqueous sodium bicarbonate solution (2 15 mL), dried over anhydrous Na2SO4 and filtered. The filtrate was evaporated under vacuum togive of methyl benzoate product (Table 3, entry 7): Colorless oil; 1H NMR (400 MHz, CDCl3):d = 7.93-7.92 (dd, J = 7.5 Hz, 2 H),7.26-7.24 (dd, J = 7.5 Hz, 2 H), 3.83 (s, 3 H), 2.62 (m, 2H), 1.25 (t,3H). 13C NMR (100 MHz, CDCl3): delta 15.2, 28.9, 51.8, 127l.7, 127.9, 129.7, 149.7,167.1 |
68% | sulfuric acid; for 5h;Heating / reflux; | Step 9. The Synthesis of Methyl 4-Vinylbenzoate (69); 69A solution of 4-vinylbenzoic acid (1.5 g, 10.1 mmol) in MeOH (150 cm3), with 3 drops of cone. H2SO4 added, was refluxed for 5 hours after which the solution was diluted with CHCI3 (150 cm3). The solution was washed with saturated NaHCO3 solution (2 x 75 cm3) to remove any acidic starting material. The aqueous layer was extracted with CHCI3 (3 x 100 cm3). The combined organics were then washed with brine (3 x 100 cm3), dried (Na2SO4) and removed solvent under reduced pressure to give off white crystals (1.22 g, 74%). Methyl 4-vinyl benzoate 69 was purified by column chromatography (DCM) and recrystallised from MeOHlambda/Vater to give white platelet shaped crystals (1.11 g, 68%) mp 35-38 C (lit.,6 35-36 0C).1H NMR (CDCI3): deltaH = 3.91 (3H, s, OCH3), 5.38 (1H, d, J 10.8, =CH2), 5.86 (1H, d, J 17.6, =CH2), 6.75 (1H1 dd, J 10.8 and 17.6, =CH-Ar), 7.46 (2H, d, J 8.4, Ar H), 8.00 (2H, d, J 8.4, Ar H)13C NMR (CDCI3): deltac = 52.1 (CH3), 116.5 (=CH2), 126.1 (CH), 129.3 (CH)1 129.9 (C*), 136.0 (CH), 141.9 (C*), 166.9 (C=O) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | Compound 12 (1.95 g, 12.0 mmol) in 1 M BH3 in THF (24 mL) was stirred 1 h at 0 C, then 1 h at ambient temperature. A solutionof 1 N NaOH (36 mL) was added to the reaction mixture at 0 C,then a solution of 35% H2O2 (20 mL) was added. The mixture was stirred 30 min at 0 C, then 30 min at ambient temperature. Ethyl acetate (100 mL) was added, the organic layer was separated,washed with water (3*50 mL), saturated Na2CO3 (3*50 mL),saturated NaCl (3*50 mL) and dried over Na2SO4. After evaporation of the solvent in vacuo, the crude product was purified by chromatography with hexane-ether (1:1) to afford 1.16 g (54%)of 13 as a colorless oil. TLC Rf 0.31 (hexane-ether 1:1); 1H NMR(300 MHz, CDCl3) delta 8.00 (d, J = 8.4 Hz, 2H), 7.32 (d, J = 8.4 Hz, 2H),3.92 (s, 3H), 3.91 (t, J = 6.6 Hz, 2H), 2.95 (t, J = 6.6 Hz, 2H). | |
1.632 g (64.7%) | In tetrahydrofuran; | Step 2 4-(2-Hydroxyethyl)benzoic Acid Methyl Ester 71 Methyl-4-vinylbenzoate 70 (2.270 g, 14.00 mmol) was dissolved in 50 ml of tetrahydrofuran and cooled to 0 C. 9-BBN (0.5M in THF)(28.00 ml, 14.00 mmol) was added and the mixture was stirred for 2 hours. The solution was allowed to warm to room temperature and stirred for an additional 2 hours. The reaction was cooled to 0 C. and quenched with alkaline hydrogen peroxide. The mixture was then extracted with diethyl ether. The extracts were dried over anhydrous sodium sulfate and concentrated en vacuo. The residue was purified by flash chromatography on silica eluted with 4:1 hexane/acetone to give 1.632 g (64.7%) of 4-(2-hydroxyethyl)benzoic acid methyl ester 71 as a clear oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
27% | With sodium hydride; In tetrahydrofuran; at 20℃; for 6h;Inert atmosphere; | Methyl-4-formylbenzoate (500 mg, 3.04 mmol, 1 equiv) and methyl triphenylphosphoniumbromide (1.09 g, 3.04 mmol, 1 equiv) were weighed into an oven-dried flask. The flask was sealed and purged with N2 before the addition of THF (15.2 mL, 0.2 M) and a solution of NaH (87.8 mg, 3.65 mmol, 1.2 equiv) in THF (7 mL). The resulting suspension was left to stir for 6 h at room temperature. After the reaction was complete, the reaction mixture was poured onto an ice/H2O slurry (30 mL), and extracted with Et2O (3 × 20 mL). The organicphase was collected and dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude residue was purified by column chromatography (silica, 0-10% EtOAc inpetroleum ether) to afford the desired product as a white solid (136 mg, 27%) |
With n-butyllithium; In hexane; | Example 77 Synthesis of 4-Ethenyl-benzoic acid methyl ester To a stirred solution of n-butyllithium (4 mL, 2,5 M solution in hexane, 10 mmol) (Aldrich) in ether (30 mL) was added methyltriphenylphosphonium bromide (3.57 g, 10 mmol) (Aldrich) over a period of 5 min. The reaction mixture was stirred for 4 h at room temperature. To the resulting orange solution was added methyl 4-formylbenzoate (1.54 mL, 10 mmol) dropwise. The solution became colorless, and a white precipitate separated. The mixture was then heated to reflux and immediately allowed to cool to room temperature. The precipitate was removed by filtration. The resulting precipitate was washed with ether, and the combined ethereal filtrates were washed with water until neutral and then dried over anhydrous MgSO4. The solvent was removed and the residue, 4-ethenyl-benzoic acid methyl ester, was used in the next reaction without further purification. | |
With nitrogen; In tetrahydrofuran; ethyl acetate; | Example 1 Preparation of Methyl p-Vinylbenzoate (MVB) To a three-neck, round-bottom flask equipped with an overhead stirrer, addition funnel, and a nitrogen inlet was added sodium hydride as a 60 percent dispersion (58.5 g, 1.46 mole). The sodium hydride was washed with THF (300 mL) then fresh THF (2000 mL) added. To the well-stirred suspension at room temperature was added methyltriphenyl-phosphonium bromide (500.1 g, 1.40 mole) over 35 minutes. After another 40 minutes of stirring, a solution of methyl p-formylbenzoate (218.9 g, 1.33 mole) in THF (600 mL) was added over 20-25 minutes. The mixture was then stirred at room temperature overnight for a total of 18 hours. The mixture was then filtered and the filtrate concentrated in vacuo. The residue was then treated with a 50 percent solution of ethyl acetate in hexanes (1400 mL) and filtered again. This filtrate was then concentrated in vacuo and placed on a large chromatography column (1400 mL of silica gel 60, 35-70 mesh packed with a 5 percent solution of ethyl acetate in hexanes) and eluted with a 5 percent solution of ethyl acetate in hexanes. The desired fractions were combined and concentrated in vacuo to provide 180.67 g (83.5 percent) of oil which slowly solidified to a white waxy solid. Proton NMR (Gemini 300 MHz in deuterochloroform): delta 7.98 (2H), 7.42 (2H), 6.72 (1H), 5.82 (1H), 5.37 (1H), 3.88 (3H). FDMS confirmed a mass of 162. |
To a stirred solution of n-butyllithium (4 mL, 2,5 M solution in hexane, 10 mmol) (Aldrich) in ether (30 mL) was added methyltriphenylphosphonium bromide (3.57 g, 10 mmol) (Aldrich) over a period of 5 min. The reaction mixture was stirred for 4 h at room temperature. To the resulting orange solution was added methyl 4-formylbenzoate (1.54 mL, 10 mmol) dropwise. The solution became colorless, and a white precipitate separated. The mixture was then heated to reflux and immediately allowed to cool to room temperature. The precipitate was removed by filtration. The resulting precipitate was washed with ether, and the combined ethereal filtrates were washed with water until neutral and then dried over anhydrous MgSO4. The solvent was removed and the residue, 4-ethenyl-benzoic acid methyl ester, was used in the next reaction without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With triethylamine; In dichloromethane; at 20℃; for 20h; | A solution of 4-vinylbenzoic acid (2.08 g, 14.0 mmol) and trimethyloxoniumtetrafluoroborate (2.60 g, 17.5 mmol) in CH2Cl2 (200 mL) was added triethylamine (1.56 g, 15.4 mmol) at ambient temperature. The reaction mixture was stirred for 20 h at ambient temperature, then washed with saturated Na2CO3 (50 mL), saturated NaCl (50 mL) and dried over Na2SO4. After evaporation ofthe solvent in vacuo, the crude product was purified by silica gel column chromatography with hexane and ether (10/1) to afford 1.72 g (76%) of 12 as a white solid which was used directly in the next step. TLC Rf 0.25 (hexane/ether 10/1); 1H NMR (300 MHz,CDCl3) delta 8.01 (d, J = 8.4 Hz, 2H), 7.48 (d, J = 8.4 Hz, 2H), 6.76 (dd,J = 17.5 Hz, J = 10.8 Hz, 1H), 5.88 (d, J = 17.5 Hz, 1H), 5.40 (d,J = 10.8 Hz), 3.93 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
33% | With potassium carbonate;palladium diacetate; triphenylphosphine; In N,N-dimethyl-formamide; at 100℃; for 96h;Cooling with liquid nitrogen; | The Synthesis of 5-[2-(4-MethoxycarbonyI-phenyl)-vinyI]-1,1,3,3-tetrame- thylisoindoline (73); 73 5-Bromo-1,1,3,3-tetramethylisoindoline (300 mg, 1.18 mmol), K2CO3 (300 mg,2.17 mmol, 1.8 equiv.), Pd(OAc)2 (6 mg, 0.027 mmol, 0.023 equiv.) and PPh3 (12 mg, 0.046 mmol, 0.039 equiv.) were placed into a Schlenk vessel, which was evacuated and flushed with argon three times. Methyl 4-vinylbenzoate (69) (240 mg, 1.47 mmol, 1.25 equiv.) and anhydrous DMF (15 cm3) were then added. The resulting solution was frozen in liquid N2, evacuated and thawed three times, the reaction was then sealed under argon and stirred at 100 0C for 96 hours. Water (~50 cm3) was added to the dark brown solution, which was then extracted with Et2O (4 x 80 cm3). The combined organic phases were washed with water (2 x 80 cm3), dried (Na2SO4) and the solvent removed under reduced pressure. The product, 5-[2'-(4"- methoxycarbonyl-phenyl)-vinyl]-1 ,1 ,3,3-tetramethylisoindoline (73) was purified by column chromatography (98 % CHCI3, 2 % MeOH) and recrystallised from EtOH, forming colourless crystals (132 mg, 33 %) m.p. 144-146 0C.1H NMR (CDCI3): deltaH = 1-47 (6H, s, CH3), 1.50 (6H, s, CH3), 1.61 (1H, br, NH), 3.92 (3H, s, OCH3), 7.11 (1H, d, J 16.1 Hz, =CH), 7.12 (1H, d, J 7.8 Hz, 7-H), 7.25 (1H, d, J 16.1 Hz, =CH), 7.28 (1H1 d, J 1.2 Hz, 4-H)1 7.42 (1H1 dd, J 1.2 Hz and 7.8 Hz, 6-H)1 7.57 (2H, d, J 8.3 Hz1 ArH)1 8.02 (2H, d, J 8.3 Hz1 ArH) ppm.13C NMR (CDCI3): deltac = 31.8 (CH3), 31.9 (CH3), 52.0 (C-1 and C-3), 62.7 (OCH3), 119.6 (=CH), 121.8 (=CH), 126.2 (C-6), 126.3 (C-4), 127.0 (C-7), 128.8 (C- 4"), 130.0 (C-2" and C-6"), 131.3 (C-3" and C-5"), 136.1 (C-5), 142.0 (C-1"), 149.3 (C- 7a), 149.5 (C-3a), 166.9 (C=O) ppm.+El MS found M+-H 334.18164 (2.79 ppm from calc. mass of C22H25NO2-H (M-H)): m/z 334 (M-H+, 14%), 320 (100), 305 (23), 304 (18), 144 (10). <n="44"/>IR (ATR) vmax: 3351 (NH), 2962 (alkyl CH3), 1719 (C=O)1 1604 (C=C), 1477 and 1435 (aryl C-C), 1178 (OCH3) cnr -1 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
32% | With potassium carbonate;palladium diacetate; triphenylphosphine; In N,N-dimethyl-formamide; at 100℃; for 166h;Cooling with liquid nitrogen; | The Synthesis of 5-[2-(4-Methoxycarbonyl-phenyI)-vinyl]-1,1,3,3-tetrame- thylisoindolin-2-yloxyl 77; 775-Bromo-1,1 ,3,3-tetramethylisoindolin~2-yloxyl (40) (200 mg, 0.74 mmol), K2CO3 (200 mg, 1.4 mmol, 1.9 equiv.), Pd(OAc)2 (4 mg, 0.018 mmol, 0.024 equiv.) and PPh3 (8 mg, 0.031 mmol, 0.042 equiv.) were placed in a Schlenk vessel, evacuated and flushed three times with argon. Methyl 4-vinyl benzoate (53) (160 mg, 0.99 mmol, 1.33 equiv.) and anhydrous DMF (10 cm3) were then added. The resulting solution was frozen in liquid N2, evacuated and thawed three times, the reaction then sealed under argon and stirred at 100 0C for 166 hours. Water (~100 cm3) was poured into the brown reaction mixture and was then extracted with Et2O (3 x 60 cm3). The combined organic phases were washed with water (2 * 60 cm3), dried (Na2SO4) and the solvent removed under reduced pressure. The crude 5-[2'- (4"-methoxycarbonyl-phenyl)-vinyl]-1 ,1 ,3,3-tetramethylisoindolin-2-yloxyl (77) was purified by column chromatography (70 % EtOAc, 30 % /7-Hexane) and recrystallised from EtOH to give light orange needles (84 mg, 32 %) m.p. 164-165 0C.+El MS found M+ 350.17546 (0.44 ppm from calc. mass of C22H24NO3): m/z 350 (M+, 30%), 335 (25), 320(100), 305 (42).IR (ATR) Vm3x: 2976 (alkyl CH), 1715 (C=O), 1604 (C=C), 1492 and 1434 (aryl C-C), 1373 and 1358 (NO), 1177 (OCH3) cm"1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
36% | With potassium carbonate;palladium diacetate; triphenylphosphine; In N,N-dimethyl-formamide; at 100℃; for 140h;Cooling with liquid nitrogen; | The Synthesis of 5,6-Bis-[2-(4-Methoxycarbonyl-phenyl)-vinyl]-1,1,3,3-tetrame- thylisoindolin-2-yloxyl 78; 78 5,6-Dibromo-1 ,1,3,3-tetramethylisoindolin-yloxyl (37) (100 mg, 0.28 mmol),K2CO3 (126 mg, 0.91 mmol, 3.27 equiv.), Pd(OAc)2 (4 mg, 0.008 mmol, 0.06 equiv.) and PPh3 (8 mg, 0.031 mmol, 0.11 equiv.) were placed into a Schlenk vessel, which was evacuated and flushed with argon three times. Methyl 4-vinylbenzoate (69) (120 mg, 0.737 mmol, 2.63 equiv.) and anhydrous DMF (5 cm3) were then added. The resulting solution was frozen in liquid N2, evacuated and thawed three times, the reaction was then sealed under argon and stirred at 100 0C for 140 hours. Water (~50 cm3) was added to the dark brown solution, followed by extraction with EtO2 (5 * 50 cm3). The combined organic phases were washed with water (2 x 50 cm3), dried (Na2SO4) and the solvent removed under reduced pressure. 5,6-Bis-[2'-(4"- methoxycarbonyl-phenyl)-vinyl]-1 ,1,3,3-tetramethylisoindolin-yloxyl (78) was purified by column chromatography (30 % EtOAc, 70 % n-Hexane) and recrystallised from MeCN to from fine light yellow needles (53.3 mg, 36 %) m.p. 212-214 0C (decomp.). +El MS found M+ 510.22812 (0.13 ppm from calc. mass of C32H32NO5): m/z 510 (M+, 15%), 495 (9), 480 (100), 465 (10), 330 (40). IR (ATR) vmax: 2973 (alkyl CH), 1708 (C=O), 1602 (C=C), 1484 and 1403 (arylC-C)1 1373 and 1359 (NO) cm"1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
11.2% | With potassium carbonate;palladium diacetate; triphenylphosphine; In N,N-dimethyl-formamide; at 100℃; for 142h;Cooling with liquid nitrogen; | The Synthesis of 5,6-Bis-[2-(4-Methoxycarbonyl-phenyl)-vinyl]-1,1,3,3-tetrame- thylisoindoline 74; 745,6-Dibromo-1 ,1,3,3-tetramethylisoindoline (300 mg, 0.90 mmol), K2CO3 (378 mg, 2.73 mmol, 3.03 equiv.), Pd(OAc)2 (12 mg, 0.054 mmol, 0.06 equiv.) and PPh3 (24 mg, 0.092 mmol, 0.10 equiv.) were placed into a Schlenk vessel, which was evacuated and flushed with argon three times. Methyl 4-vinylbenzoate (69) (360 mg, 2.21 mmol, 2.46 equiv.) and anhydrous DMF (15 cm3) were then added. The resulting solution was frozen in liquid N2, evacuated and thawed three times, the reaction was then sealed under argon and stirred at 100 0C for 142 hours. Water (~50 cm3) was added to the dark brown solution, which was then extracted with Et2O (6 x 70 cm3). The combined organic phases were washed with water (2 * 80 cm3), dried (Na2SO4) and the solvent was removed under reduced pressure. 5,6-Bis-[2'-(4"- methoxycarbonyl-phenyl)-vinyl]-1,1,3,3-tetramethylisoindoline (74) was purified by column chromatography (70 % EtOAc, 30 % n-Hexane; then 80 % EtOAc1 20 % EtOH) and recrystallised by mixed solvent layer recrystallisation from DCM/n- pentane, forming off-white crystals (49.9 mg, 11.2 %) m.p. 176-178 0C.1H NMR (CDCI3): deltaH = 1.53 (12H, s, CH3), 1.74 (1H, br, NH), 3.93 (6H, s, OCH3), 7.04 (2H, d, J 15.8 Hz, =C-H), 7.34 (2H, s, 4-H and 7-H)1 7.57 (2H1 d, J 15.8 Hz1 =C-H), 7.59 (4H1 d, J 8.2 Hz, ArH), 8.04 (4H, d, J 8.2 Hz, ArH) ppm.13C NMR (CDCI3): deltac = 31.7 (CH3), 52.1 (C-1 and C-3), 62.9 (OCH3), 119.8 (=CH), 119.9 (=CH), 126.4 (C-4 and C-7), 129.1 (C-2" and C-6"), 130.1 (C-3" and C- <n="45"/>5"), 130.3 (C-4"), 135.4 (C-5 and C-6), 141.8 (C-1"), 149.3 (C-3a and C-7a), 166.8 (C=O) ppm.+El MS found M+-H 494.23332 (0.38 ppm from calc. mass of C32H33NO4-H (M-H)): m/z 494 (M-H+, -1%), 480 (100), 465 (8), 320 (24). IR (ATR) vmax: 3345 (NH), 3018 (aryl CH), 2955 (alkyl CH), 1708 (C=O), 1603(C=C), 1479 and 1433 (aryl C-C), 1178 (OCH3) cm 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With triethylamine;tris-(dibenzylideneacetone)dipalladium(0); tris-(o-tolyl)phosphine; In DMF (N,N-dimethyl-formamide); at 100℃; for 12h; | Step 2; methyl 4-[(Emethyl 4-[(tert-butyl(dimethyl)silyl]oxy}pyridin-2-yl)vinyl]benzoate; To a solution the TBS ether from step 1 (10 g, 34.7 mmol) in DMF (50 ml) was added <strong>[1076-96-6]4-vinylbenzoic acid methyl ester</strong> (6.2g, 38.2 mmol) and the solution was degassed with nitrogen for 5 minutes. Triethylamine (5.37 mL, 38.2 mmol), tri (o-tolyl)phosphine g, 6.94 mmol) and tris (dibenzylideneacetone) dipalladium (3.18 g, 3.47 mmol) were then added and the mixture was stirred at 100 C for 12 h. The reaction was cooled to rt., water (500mL) was added and the product was extracted with 9:1 hexanes: CH2Cl2. The combined extracts were dried over Na2S04 and concentrated. The title product (9 g, 70%) was obtained after purification by flash chromatography on silica using 10-30% EtOAc/hexane as eluent. MS (+ESI) 371.0. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With triethylamine; tris-(o-tolyl)phosphine;palladium diacetate; In N,N-dimethyl-formamide; at 85℃; | To a stirred solution of (Z)-1,3-dihydro-4-iodo-3-[(3-methoxy-1H-pyrrol-2-yl)methylene]-2H-indol-2-one(100 mg, 0.29 mmol) (Starting Material 2) in DMF (3 mL) and TEA (2 mL) was added 4-ethenyl -benzoic acid methyl ester (0.11 mL, 0.58 mmol)(from Example 77 above), tri-o-tolylphosphine (107 mg, 0.35 mmol) (Aldrich) and Pd(OAc)2 (20 mg, 0.089 mmol) (Aldrich). The reaction mixture was stirred at 85 C overnight in a pressure tube. The solvent was removed in vacuo, and the residue was purified by silica gel chromatography (Hex:EtOAc = 5:1) to provide 4-[(E)-2-[2,3-dihydro-(Z)-3-[(3-methoxy-1H-pyrrol-2-yl)methylene]-2-oxo-1H-indol-4-yl]ethenyl]benzoic acid methyl ester as a yellow solid. (Yield 77 mg, 66%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 61% 2: 43% | With dichloro bis(acetonitrile) palladium(II); 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In tetrahydrofuran; acetonitrile at 20℃; for 14h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 72% 2: 17% | With dichloro bis(acetonitrile) palladium(II); 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In tetrahydrofuran; acetonitrile at 20℃; for 14h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With iodoform; [bis(acetoxy)iodo]benzene; In 1,4-dioxane; at 20℃;Irradiation; | General procedure: A 5 mL oven-dried reaction vessel equipped with a magnetic stirrer bar was charged with styrene (1a, 20.8 mg,0.20 mmol), PhI(OAc)2 (32.1 mg, 50 mol%), CHI3 (2a, 0.20 mmol) and dioxane (2.0 mL). The reaction vessel wasexposed to sunlight at room temperature in air with stirring for 6 h. After completion of the reaction, the mixture wasconcentrated to yield the crude product, which was further purified by flash chromatography (silica gel, petroleumether/ethyl acetate = 10:1 to 5:1) to give the desired product 3a. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With tetra-(n-butyl)ammonium iodide; triethylamine;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In water; N,N-dimethyl-formamide; at 20℃; | Intermediate 174-{(E)-2-[4-Cyclohexylamino-1-(4-methoxy-benzyl)-1H^yrazolo^benzoic acid methyl esterTo a mixture of Intermediate 16 (0.25 g, 0.54 mmol) and tetrabutylammonium iodide (0.4 g, 1.08 mmol) in DMF/water/triethylamine (5 ml/0.75 ml/0.75 ml) at room temperature was added methyl-4-vinyl benzoate (0.44 g, 2.7 mmol) and [1 , 1 - bis(diphenylphosphino)ferrocene]palladium(ll) chloride (88 mg, 0.1 1 mmol) respectively. The resulting mixture was heated at 70 C overnight and then evaporated to dryness. The crude residue was dissolved in EtOAc and washed with water. The organic phase was collected, dried (MgS04) and then evaporated. The crude residue was purified by flash chromatography, eluting with 10 to 100% ethyl acetate/petroleum ether gradient to give the desired product as a brown solid (190 mg, 70 %). 1H NMR (400 MHz, DMSO-dB) delta ppm 1.15 - 1.24 (m, 1 H), 1.27 - 1.48 (m, 4 H), 1.59 - 1.65 (m, 1 H), 1.70 - 1.77 (m, 2 H), 1.94 - 2.01 (m, 2 H), 3.69 (s, 3 H), 3.86 (s, 3 H), 4.03 - 4.11 (m, 1 H), 5.47 (s, 2 H), 6.14 (d, J=7.8 Hz, 1 H), 6.85 - 6.90 (m, 3 H), 7.19 - 7.23 (m, 2 H), 7.45 (d, J=16.0 Hz, 1 H), 7.73 - 7.82 (m, 2 H), 7.85 (d, J=8.2 Hz, 2 H), 7.98 (d, J=8.7 Hz, 2 H);m/z (ES+APCI)+: 497 [M + Hf |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With formic acid; iron(II) tetrafluoroborate hexahydrate; tris(2-diphenylphosphinoethyl)phosphine In tetrahydrofuran at 40℃; for 5h; Inert atmosphere; | |
90% | With C14H29BrMnNO2P2; potassium-t-butoxide; hydrogen In n-heptane at 60℃; for 16h; | |
90% | With hydrogen; tetraphenylphosphonium iodide In tetrahydrofuran at 75℃; Glovebox; | 7 Example 7 In a glove box, accurately weigh N,N-dimethylformamide (32 mg, 0.2 mmol) and put it into a reaction tube with a stirring bar, weigh tetraphenylphosphine iodide (4.6 mg, 0.01 mmol) ), take 2 ml of tetrahydrofuran with a pipette, pass 1.5 MPa of hydrogen gas, and place it in a magnetic stirrer to stir the reaction at 75 degrees Celsius. After the reaction was completed, the reactor was opened and the volatile substances were removed using a rotary evaporator under reduced pressure, and ethyl acetate and petroleum ether were used as eluents to purify by column chromatography to obtain methyl 4-vinylbenzoate ( 28.0 mg, 90% yield). |
89% | With water monomer; zinc(II) iodide; zinc powder In 1,4-dioxane at 90℃; for 24h; Inert atmosphere; Schlenk technique; Green chemistry; | |
88% | With silver(I) tetrakis(3,5-bis(trifluoromethyl)phenyl)borate; C19H13I2N3O2Ru; hydrogen In isopropanol at 80℃; for 4h; Autoclave; Schlenk technique; chemoselective reaction; | |
84% | With water monomer; zinc(II) iodide; zinc powder In N,N-dimethyl-formamide at 90℃; Inert atmosphere; | 19 Example 19 In an anhydrous and oxygen-free glove box under an argon atmosphere, add ZnI2 (0.01mmol), Zn (0.3mmol) and methyl 4-ethynylbenzoate (0.2mmol) to a 10mL reaction tube, and then add 2ml DMF (N,N-dimethylformamide), then add water (1.0mmol) and send it out of the glove box. The reaction was carried out in an oil bath at 90. The progress of the reaction was monitored by TLC monitoring and I2 color development. After the reaction was completed, the organic phase was extracted and concentrated by adding water, and the column was passed through silica gel to obtain a styrene compound, a pale yellow liquid, with a yield of 84% . |
63% | With hydrogen In glycerol at 100℃; for 24h; chemoselective reaction; | |
66 %Spectr. | With hydrogen In acetonitrile at 100℃; for 8h; Autoclave; Sealed tube; | |
99.1 %Chromat. | With PdC0.18; hydrogen In toluene at 30℃; for 0.25h; | |
With hydrogen In methanol at 20℃; for 1h; Autoclave; | ||
With hydrogen In cyclohexane at 79.84℃; for 1.33333h; Autoclave; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With N-benzyl-9,10-dioxo-9,10-dihydroanthracene-2-carboxamide; oxygen; barium(II) hydroxide; In N,N-dimethyl acetamide; at 20℃;Irradiation; | General procedure: A Pyrex test tube (16.5 cm 1.5 cm) containing a solution of 4-tertbutylstyrene (1a) (48.1 mg, 0.3 mmol, 1.0 equiv), sodium trifluoromethanesulfinate (93.6 mg, 0.6 mmol, 2.0 equiv), AQN-2-CONHBn (3e) (20.6 mg, 0.06 mmol, 0.2 equiv), Ba(OH)2 (51.4 mg, 0.3 mmol, 1.0 equiv) and dry DMA (4 mL) was equipped with an O2 balloon. The stirred reaction mixture was irradiated for 30 h at room temperature by a 21 W fluorescent lamp placed at a distance of 5 mm. The mixture was diluted with Et2O (10 mL) and H2O (10 mL) and the aqueous layer extracted with Et2O (3 10 mL). The combined organic layers were washed with brine, dried over MgSO4 and concentrated in vacuo. Purification of the residue by flash chromatography on silica gel (hexane/ EtOAc, 94:6) provided 1-[4-(tert-butyl)phenyl]-3,3,3-trifluoropropan-1-one (2a) (60.0 mg, 0.25 mmol, 82%) as a white solid. Mp 35-37 C; Rf = 0.4 (n-hexane/EtOAc, 16:1). IR (neat): 2963, 1692, 1232 cm-1. 1H NMR (500 MHz, CDCl3): delta = 7.89 (d, J = 8.6 Hz, 2 H), 7.53 (d, J = 8.6 Hz, 2 H), 3.79 (q, J = 10.1Hz, 2 H), 1.36 (s, 9 H). 13C NMR (125 MHz, CDCl3): delta = 189.3, 158.2, 133.2, 128.4, 125.8, 124.0 (q, J = 275.4 Hz), 41.9 (q, J = 28.6 Hz), 35.2, 31.0. 19F NMR (470 MHz, CDCl3): delta = -61.87 (t, J = 10.8 Hz, 3 F). MS (EI+): m/z = 244.11 [M]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83.1% | With tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride; In dichloromethane; at 40℃;Inert atmosphere; | To a stirred solution of [(2R,3R,4R,5R,6R)-3,5-diacetoxy-6-allyl-4- [(2R,3S,4S,5R,6R)-3,4,5-triacetoxy-6-(acetoxymethyl)tetrahydropyran-2-yl]oxy- tetrahydropyran-2-yl] methyl acetate (Compound 281, Step I) (50 mg, 0.07569 mmol) in DCM (5 mL) are added <strong>[1076-96-6]methyl 4-vinylbenzoate</strong> (49.11 mg, 0.3028 mmol) and Grubbs catalyst II (6.2 mg, 0.0075mmol) . The mixture is stirred at 40 C under nitrogen overnight. After removal of the solvent under reduced pressure, the residue is purified on Biotage SNAP 10 g silica gel cartridge using a gradient of MeOH/DCM (0-5% in 20 CV) to afford the title compound (50 mg, 83.1%). LC-MS: m/z = 817.3 (M+Na+). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With bromine; In chloroform; at 0 - 20℃; for 1h;Inert atmosphere; | General procedure: For example the preparation of 1-(1,2-dibromoethyl)-4-methylbenzene (S5)-Bromine (260 muL, 5.07 mmol, 1.2 equiv) was added dropwise to a stirred solution of 4-methylstyrene (500 mg, 4.23 mmol, 1 equiv) in CHCl3 (8.5 mL, 0.5 M) at 0 C under N2 atmosphere. After 5 min the reaction mixture was allowed to warm to room temperature and was stirred for 1 h. After the reaction was complete, the reaction mixture was quenched with saturated aqueous Na2S2O3 (15 mL) and diluted in CH2Cl2 (20 mL). The organic phase wasthen separated, washed with H2O (20 mL) and brine (20 mL), dried over Na2SO4, filtered,and concentrated under reduced pressure, to afford the desired product as a white solid (1.2 g,yield quant.). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline)CuBr; In dimethyl sulfoxide; at 20℃; for 0.5h;Inert atmosphere; | General procedure: General procedure A: To a dried glass tube, Togni reagent 2 (99mg, 0.3mmol, 1.5equiv), (L3)CuBr (10mg, 0.02mmol, 0.1equiv) and DMSO (1.0mL) were added under N2 atmosphere, followed by substrate 1 (0.2mmol, 1.0equiv) and TMSCN (54muL, 0.4mmol, 2.0equiv). After the reaction mixture was stirred at room temperature for 0.5h, dichloromethane was added and the mixture was filtered through a short pad of celite. The filtrate was washed with water (15mL×3) and dried over anhydride Na2SO4. After the removal of solvent, the residue was purified by column chromatography on silica gel with a gradient eluent of petroleum ether and ethyl acetate to afford the product. General procedure A: Pale yellow liquid; 38.1mg, 74%; 1H NMR (400MHz, CDCl3): delta 8.09 (d, J=8.0Hz, 2H), 7.46 (d, J=8.0Hz, 2H), 4.17 (dd, J=8.8, 5.2Hz, 1H), 3.93 (s, 3H), 2.95-2.77 (m, 1H), 2.70-2.55 (m, 1H); 13C NMR (100MHz, CDCl3): delta 166.1, 138.0, 131.0, 130.8, 127.4, 124.5 (q, J=276.3Hz), 117.9, 52.4, 39.4 (q, J=30Hz), 31.2 (q, J=3.1Hz); 19F NMR (376MHz, CDCl3): delta -64.9 (t, J=9.4Hz); HRMS (EI), calcd. for C12H10F3NO2 257.0664 [M]+, found 257.0668. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
803 mg | A similar procedure as described above for methyl 4-(2-(3-(3,5-dimethoxybenzyl)-lH-inden-4-yl)ethyl)benzoate was followed using methyl 4-vinyl benzoate (500 mg, 3.08 mmol) and 9-BBN dimer (755 mg, 3.09 mmol) in THF (12 mL) followed by 7-bromo-2,3-dihydro-lH-inden-l-one (503 mg, 2.38 mmol), PdCl2(dppf)-CH2Cl2 (177 mg, 0.24 mmol) and 3 M K3P04 solution (1.1 mL, 3.3 mmol) in 7.6 mL DMF. This gave the title compound (803 mg, >100%>) which was used in the next step |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With potassium carbonate; In acetonitrile; at 20℃; | General procedure: To a round-bottom flask (25mL), 1 (0.5 mmol), 2 (0.5 mmol), K2CO3 (1.0 mmol), and solvent (5mL) were added. After stirring at room temperature overnight, the reaction mixture was evaporated under reduced pressure, and the residue was separated by preparative TLC (silica gel, eluted with PE or PE/EtOAc 50:1) to afford the alkene 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86.4% | With Hoveyda-Grubbs catalyst second generation; In dichloromethane; at 60℃; for 48h; | A solution of cyclosporine A (1.00 g, 0.832 mmol), methyl-4-vinylbenzoate (270 mg, 1.665 mmol) and Hoveyda-Grubbs 2? generation catalyst (20 mg, 0.03 2, 4%) in dichloromethane (4 ml) was stirred at reflux (60C) under nitrogen for 48 hours. T.l.c.analysis (acetone: cyclohexane, 1 : 1) of the reaction mixture showed the presence of theproduct (Rf 0.63) and complete consumption of the cyclosporine A starting material (Rf 0.65). LCMS analysis also confirmed the presence of the product. The reaction mixture was pre-absorbed on silica gel and purified by flash column chromatography (ethyl acetate: cyclohexane, 1: 1 to ethyl acetate to ethyl acetate: methanol, 10%) and thesolvent removed in vacuo to give a grey solid. The grey solid was then further purified by removing the Grubbs-Hoveida catalyst by letting it through an SPE-thiol column (eluant:methanol). The solvent was removed in vacuo to give the corresponding methyl ester as a white crystalline solid (950 mg, 86.4%).HRMS (TOF MS ES): found 1344.8726 [M+Na] C69H115N11O14Na requires1344.8523. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With [i-PrNDI]Ni2(C6H6); zinc In N,N-dimethyl acetamide at 22℃; for 65h; Inert atmosphere; Glovebox; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With tert.-butylhydroperoxide; toluene-4-sulfonic acid; In decane; 1,2-dichloro-ethane; at 60℃; for 4h; | General procedure: To a solution of N-hydroxyphthalimide (2, 0.3 mmol, 48.9 mg) and TEMPO (0.6 mmol, 93.6 mg) in DCE (2.0 mL) was added styrene (1, 0.45 mmol), TsOH (10%, 0.03 mmol, 5.2 mg), TBHP (3.0 equiv, 150 mL, 5-6 M in decane). The reaction mixture was then stirred for 4 h at 60 C in air. After the reaction, the resulting mixture was quenched with water and extracted twice with EtOAc (10 mL). The combined organic extracts were washed with brine (10 mL), dried over Na2SO4 and concentrated. Purification of the crude product by flash column chromatography afforded the product 3 (petroleum ether/ethyl acetate as eluent (10:1)). 4.2.5 Methyl 4-(2-(1,3-dioxoisoindolin-2-yloxy)-1-(2,2,6,6-tetramethylpiperidin-1-yloxy)ethyl)benzoate, 3e Mp=100-102 C, 1H NMR (400 MHz, CDCl3): 7.70-7.78 (m, 2H), 7.50 (d, J=8.0 Hz, 2H), 7.09 (d, J=8.0 Hz, 2H), 5.14-5.17 (m, 1H), 4.72-4.74 (m, 1H), 4.44-4.49 (m, 1H), 2.3 (s, 3H), 1.05-1.47 (m, 16H), 0.74 (m, 2H); 13C NMR (100 MHz, CDCl3): 169.0, 163.0, 150.1, 137.5, 134.3, 128.8, 128.6, 123.2, 120.9, 82.4, 79.9, 59.9, 40.2, 33.9, 33.8, 20.9, 20.1, 16.9; IR (cm-1): 2973, 2933, 1790, 1731, 1506, 1467, 1372, 1131, 1081, 1017, 877, 701; HRMS (ESI) m/z: calcd for C27H32N2O6Na+: [M+Na+]=503.2158; found: 503.2156. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With manganese(II) acetate; copper(I) bromide; In acetonitrile; at 50℃;Inert atmosphere; | The reaction procedure is as follows: 4-vinylbenzoate, diphenylphosphine oxide as raw material,A solution of <strong>[1076-96-6]methyl 4-vinylbenzoate</strong> (0.065 g, 0.4 mmol), diphenylphosphine oxide (0.162 g, 0.8 mmol), trimethylcyanosilane (0.079 g, 0.8 mmol), CuBr (0.168 G, 0.12 mmol), manganese acetate (0.322 g, 1.2 mmol) and acetonitrile (3 mL) under argon at 50 C;TLC tracks the reaction until it ends completely;The crude product obtained after the completion of the reaction was separated by column chromatography (ethyl acetate: petroleum ether = 1: 1) to give the desired product (yield 84%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With tetrakis(actonitrile)copper(I) hexafluorophosphate; C27H28N2O2; lithium tert-butoxide; In dichloromethane; N,N-dimethyl acetamide; at -20 - -10℃; for 96h;Inert atmosphere; Sealed tube; | General procedure: Step1; In a 100 mL sealed tube, ligand L * (82.0 mg, 0.20 mmol) and Cu (CH3CN) 4PF6 (37.0 mg, 0.10 mmol) under argon, was dissolved in DMA / CH2Cl2 (1: 4, 20 mL) and stirred for 0.5 hour. The resulting colorless solution was allowed to stand.Step 2: The compound of formula III (0.40 mmol, 2.0 equiv) and anhydrous LiOtBu (8.0 mg, 0. Lmmol, 0.5 equiv) were added to a 10 mL sealed tube. Under argon protection, the copper catalyst solution (2.OmL) was added to the reaction vessel at -20 C, followed by the compound of formula II (0.20 mmol, 1. Equiv) as shown in Formula I (0 · 4 mmol, 2. Oequinu), the reaction solution became blue. The reaction was stirred at -10 C. After a specified time, the reaction was diluted with 20 mL of ethyl acetate and washed with water (10 mL X 3). The organic phase was dried over anhydrous MgS04 and filtered. The filtrate was concentrated and the column was separated by flash column chromatography (petroleum ether / ethyl acetate, and the ratio of the compound was selected according to the specific TLC). The desired product was purified by HPLC Determination of column resolution. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With 1,4-diaza-bicyclo[2.2.2]octane; tert.-butylnitrite; copper(II) acetate monohydrate; In toluene; at 80℃; for 0.12h;Sealed tube; | The reaction flask was charged with Cu (OAc) 2.H2O (10 mol%), DABCO (3 mmol), toluene 15 mL, compound 1i(3 mmol), compound 2a (6 mmol), t-butyl nitrite 3 (6 mmol), and then the system was sealed at 80 CAfter heating for about 12 hours, the mixture was extracted with ethyl acetate (20 mL x 3), washed three times with saturated brine, dried over anhydrous sodium sulfateThe organic layer was purified by a simple column chromatography to give the product 4i in 72% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With dicyclohexyl(2',4',6'-triisopropyl-[1,1':3',1''-terphenyl]-2-yl)phosphane; tetrabutylammomium bromide; palladium diacetate; potassium carbonate In N,N-dimethyl-formamide at 90℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | General procedure: To a solution of methyltriphenylphosphonium iodide (22.61mmol; 1.2equiv) in dry DME (50mL), K2CO3 (28.26mmol; 1.5equiv) was added in several portions, and stirring under argon was continued for 1h. Then the aldehyde (18.84mmol; 1equiv) was added and stirring was continued for overnight at 80C. After cooling, 30mL of diethyl ether was added to precipitate the insoluble salts. The mixture was collected by suction filtration, washed with ether, and the solvents were evaporated under reduced pressure. The crude product was purified by chromatography on silica gel using cyclohexane as an eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With trans-di(mu-acetato)bis[o-(di-o-tolylphosphino)benzyl]dipalladium(II); sodium acetate; In N,N-dimethyl acetamide; at 100 - 140℃; for 48h;Schlenk technique; Inert atmosphere; | General procedure: A solution of aryl halide 7a-c (6.37mmol; 1equiv) anddry NaOAc (7.64mmol; 1.2equiv) in N,N-dimethylacetamide (3mL) was placed in a Schlenk tube and repeatedly degassed and purged with argon five times. The styrene derivative 6a-d (1.4equiv) was added and the mixture was heated to 100C. Next, a solution of Herrmann's catalyst (59.68mg, 1mol%) in N,N-dimethylacetamide (2mL) was added and the mixture was heated to 140C during 48h. The product was worked up by addition of H2O and the organic phase was extracted with EtOAc (3×30mL). The combined organic phases were dried over MgSO4. After removal of the solvent, the residue was purified by silica gel column chromatography with cyclohexane/EtOAc (98:02) as the eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With tris(bipyridine)ruthenium(II) dichloride hexahydrate; In acetonitrile; at 20℃; for 4h;Irradiation; Inert atmosphere; | General procedure: A 10 mL reaction vessel with a magnetic stirring bar wasequipped with sulfonyl chloride(0.5 mmol), alkene (0.5 mmol), Ru(bpy)3Cl2·6H2O (1mol%), and acetonitrile (2 mL). The mixture was irradiated with a blue LED (5 W)and stirred under at r.t. in an air atmosphere for 4h. The distance of the reaction vialfrom the light is about 2 centimeter. After the reaction, the solvent was removed underreduced pressure. Purification of the crude product was achieved by flash columnchromatography using petrol ether/ethyl acetate (6:1~10:1) as eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With tetrakis(actonitrile)copper(I) hexafluorophosphate; iodosylbenzene In acetonitrile at 0 - 20℃; Molecular sieve; | 1. Preparation of aziridines Method A General procedure: A 100 ml round-bottom flask equipped with a magnetic stirring bar was charged with TsNH2 (7 mmol, 1.4 equiv), Cu(MeCN)4PF6 (0.5 mmol, 0.1 equiv), alkene (5 mmol, 1.0 equiv), activated 3 Å molecular sieves (5 g, 1.0 g/mmol alkene), and MeCN (50 ml, 10 mL/mmol alkene). The mixture was cooled in a 0 oC ice-water bath, and PhI=O (7 mmol, 1.4 equiv) was added in one portion. The mixture was allowed to warm up to room temperature and stirred for overnight. The resulting mixture was filtered through Celite, and the filtrate was concentrated. The crude was purified by flash column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
32% | With tris(2,2-bipyridine)ruthenium(II) hexafluorophosphate; silver fluoride; 1-azido-1λ3-benzo[d][1,2]iodaoxol-3(1H)-one; 4,4',4-tri-tert-butyl-2,2':6',2-terpyridine In acetonitrile at 10℃; for 4h; Inert atmosphere; Glovebox; Sealed tube; Irradiation; | |
32% | With tris(2,2-bipyridine)ruthenium(II) hexafluorophosphate; silver fluoride; 1-azido-1λ3-benzo[d][1,2]iodaoxol-3(1H)-one; 4,4',4-tri-tert-butyl-2,2':6',2-terpyridine In acetonitrile at 20℃; for 4h; Inert atmosphere; Sealed tube; Irradiation; | 71 Example 6 1-(2-azido-1-(trifluoromethoxy)ethyl)-2,4,6-trimethylbenzene (4a) General procedure: Under the protection of N2, Ru(bpy)3(PF6)2 (2.4 mg, 0.00300 mmol, 1.0 mol%), AgF (19.2 mg, 0.150 mmol, 50.0 mol%) was added to the sealed tube. 4,4',4"-tri-tert-butyl-2,2':6',2"-terpyridine (tbtpy, 36.0 mg, 0.0900 mmol, 30.0 mol%),1-azido-1,3 benzo[d][1,2]iodohydroxy-3(1H)-one (3) (173.4 mg, 0.600 mmol, 2.00 eq.), then acetonitrile solvent (2.40 mL) ,4-phenylstyrene (1a) (43.9 mg, 0.300 mmol, 1.00 equiv), trifluoromethyl 4-methylbenzenesulfonate (2) (169 μL, 0.9 mmol, 3.00 equiv) was added to the reaction. The resulting mixture was then allowed to stand at room temperature and stirred under irradiation with a 14 W blue LED for 4 hours.After that, the reaction mixture was concentrated in vacuo and purified by silica gel chromatography.Elution with petroleum ether / ethyl acetate 100:1 (v / v) gave the corresponding product (4a), 65.5mg. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With Fmoc-Val-OH; silver(I) acetate; palladium diacetate; In 1,4-dioxane; at 120℃; for 12h;Inert atmosphere; Sealed tube; | General procedure: Pd(OAc)2 (1.9 mg, 0.0085mmol, 10 mol%) Ag2CO3 (35.3 mg, 0.128 mmol, 1.5 equiv.), quinoxaline N-oxide (50 mg, 0.342 mmol, 4 equiv) and Fmoc-Val-OH (0.0138, 0.0855 mmol, 1 equiv) were added to 1 mL amber screw-capped vial, equipped with a stirring bar. Following addition of solid compounds, the vial was hermetically sealed with Teflon-lined cap, and the reaction medium was purged with nitrogen. Previously dried 1,4-dioxane (0.5 mL) and the alkene (0.0855 mmol) were added into solid mixture, with syringe assistance. The reaction mixture was stirred at 120 C for 12 hours. The reaction was cooled until room temperature, filtered by assistance of a plug of celite, washed with ethyl acetate (30 mL), the solvent was removed under reduced pressure. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With pyridine; copper dichloride; In 1,4-dioxane; at 100℃; for 1h;Inert atmosphere; Schlenk technique; | General procedure: CuCl2 (7 mg, 10 mol%), alkene (0.5 mmol), 1,4-dioxane (2 mL), CF3SO2Cl (152 mg, 1.8 eq.) and pyridine (4 mg, 10 mol%) were added into a Schlenk tube under a N2 atmosphere. The reaction mixture was stirred at 100 C for 1 h. After being cooled to room temperature, the solid was removed by filtration and washed with DCM (30 mL). The combined organic solution was evaporated, and the resulting crude product was purified by flash column chromatography to give the products 3 or 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With C38H55F3GeO3P2PdS In N,N-dimethyl-formamide at 100℃; for 6h; Inert atmosphere; | 2 [Example of Hydrocarboxylation Reaction of the Present Invention] Under a nitrogen atmosphere,Complex 2 (2.2 mg, 0.0025 mmol),Cesium formate (26.7 mg, 0.15 mmol),Methyl p-vinylbenzoate (16.2 mg, 0.1 mmol),N, N-dimethylformamide (2 mL) was added to a glass reaction vessel,And heated at 100 ° C. for 6 hours.After cooling, hydrochloric acid (2 N, 2 ml, 2 mmol) was added,Extraction was carried out by adding diethyl ether (4 ml, 38.5 mmol)After desolvation under reduced pressure, 1 H-NMR was measured,From the ratio to the internal standard substance tetrachloroethane,It was confirmed that the product 3 was produced in a yield of 64 mol%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With dipotassium hydrogenphosphate; [4,4?-bis(1,1-dimethylethyl)-2,2?-bipyridine-N1,N1?]bis [3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-N]phenyl-C]iridium(III) hexafluorophosphate; triphenylphosphine; In dichloromethane; water; at 20℃;Inert atmosphere; Irradiation; | Firstly weighing (27.2 mg, 0.2 mmol),photocatalyst Ir[dF(CF3)ppy]2(dtbbpy)PF6(2.3 mg, 0.002 mmol), K2HPO4(7.0 mg, 0.04 mmol), and Ph3P (62.9 mg, 0.24 mmol) are added to a reaction tube, pumping air through the vacuum line three times, in the argon atmosphere, adding DCM/H2O (2.0 ml, 4:1 v/v), then carefully added (48.6 mg, 0.3 mmol),then put into 5 W blue LEDs lamp irradiation, react at room temperature for 36 - 60 h. Add 20 ml water, and the DCM extraction (3x 10 ml) the aqueous phase, combined with the organic phase. The organic phase by absolute Na2SO4 after drying and steaming and to remove the solvent, dry sample, column chromatography (300 - 400 item of chromatographic analysis silica gel) (petroleum ether - ethyl acetate) to obtain the product 37.8 mg, Yield 67%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; copper(I) thiocyanate; CyJohnPhos; lithium tert-butoxide; In 1,2-dichloro-ethane; at 20 - 80℃;Inert atmosphere; Schlenk technique; | First, add a suitable size stirrer to the pre-dried 25 ml Schlenk and replace the nitrogen three times.CuSCN (10 mol%, 3.7 mg), CyJohn Phos (22 mol%, 48.3 mg) and solvent DCE were sequentially added under a nitrogen atmosphere.(1 mL), stir at room temperature until the solution turned from white to colorless. Continue to feed LiOtBu (1 eq., 0.3 mmol, 24 mg) in sequence.Methyl 4-vinylbenzoate(1 eq., 0.3 mmol, 48.6 mg), TEMPO (2 eq., 0.6 mmol,93.6 mg), diboronic acid pinacol ester (2 eq., 152.3 mg) and finally solvent DCE (1 mL). Warming up to 80 degrees,The reaction was monitored by TLC until the end of the reaction.After stopping the reaction, it was cooled first and then extracted three times with ethyl acetate.The mixture was dried over anhydrous sodium sulfate, then adsorbed with 100-200 mesh silica gel, and then rinsed through a column of 300-400 mesh silica gel (pre-added one-thousandth of boric acid) to obtain a product 3k in a yield of 84%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With copper(l) iodide; tert-Butyl peroxybenzoate; trimethylsilylazide; In acetonitrile; at 50℃; for 6h;Schlenk technique; Inert atmosphere; Green chemistry; | General procedure: Adding a compound containing carbon-carbon double bonds (1 equivalent) to the Schlenk tube, CuI (10 mol%),TMSN3 (212 mg, 1.75 mmol, 3.5 equivalents), TBPB (149 mg, 0.75 mmol, 1.5 eq.) and CH3CN (2 mL) were stirred under nitrogen atmosphere at 50 C for 6 hours and then cooled to room temperature. The mixture was extracted with a saturated NaHCO3 solution and ethyl acetate. The organic phase was evaporated on a rotary evaporator, and the silica gel was passed through a column to obtain a diazide compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With 1,1'-bis-(diphenylphosphino)ferrocene; nickel(II) bromide dimethoxyethane; 1,1,1,3',3',3'-hexafluoro-propanol; zinc In tetrahydrofuran at 25℃; for 12h; Inert atmosphere; | 4.1. General procedure for the alkylation reaction General procedure: A 2 mL crimp-top GC vial was charged with NiBr2(DME) (6.2 mg, 0.02 mmol, 0.1 equiv), dppf (11 mg, 0.02 mmol, 0.1 equiv), and activated Zn powder [35] (26.2 mg, 0.4 mmol, 2 equiv). The vial was crimped shut and the olefin (0.2 mmol, 1 equiv) was injected through the septum as a solution in 0.3 mL THF followed by 0.2 mL HFIP. The iodide (1-2 equiv) was then added (as a solution in THF, if solid) and the vial was shaken at 1000 rpm for 12 h at 25 °C. The reaction was diluted with EtOAc and quenched by the addition of 1 M HCl (aq). The aqueous phase was extracted with three portionsof EtOAc. The combined organic phase was then passed through a plug of silica. An aliquot of the organic phase was used for GC or GC/MS analysis with mesitylene as an internal standard. Solvent was removed and the mixture was purified by chromatography on silicagel with EtOAc/hexane as the eluent to give the products as colorless oils. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With copper(l) iodide; palladium diacetate; In dimethyl sulfoxide; at 80℃; for 2h; | General procedure: A mixture of styrene (0.102 g, 1.0 mmol), TosMIC (0.195 g, 1.0 mmol) and Pd(OAc)2 (0.022 g, 0.1 mmol) and CuI (0.019 g, 0.1 mmol) was stirred in DMSO (2 mL) at 80 oC for 2 h. After the reaction was complete, the mixture was quenched with a cold water. Then the solution was extracted with EtOAc (2 x 20 mL). The combined organic layers were dried with anhydrous Na2SO4 and the solvent was removed under reduced pressure. The resulting crude product was purified by flash column chromatography on silica gel (eluent: petroleum ether) to provide pure stillbene (0.17 g, 89% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
9% | With bis(cyclopentadienyl)dihydrozirconium; In toluene; at 100℃; under 760.051 Torr;Inert atmosphere; | Into the reaction tube were added <strong>[1076-96-6]methyl 4-vinylbenzoate</strong> 1w (0.2 mmol, 32 muL), pinacol borane 2a (0.2 mmol, 29 muL), toluene (1 mL), Cp2ZrH2(0.01 mmol, 2.3 mg), and stirred at 100 C under a nitrogen (1 atm) atmosphere.GC detection showed that the yield of p-methyl styrene borate pinacol ester 3w was 9%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With potassium methanolate; C29H43Br2N2NiO3P; In toluene; at 130℃; for 60h;Inert atmosphere; | Under the protection of argon, the catalyst (71.8 mg, 0.10 mmol, 20 mol%) was added to the reaction bottle in order,Potassium methoxide (35.1 mg, 0.5 mmol), N-methylindole-3-carboximide (132.2 mg, 0.5 mmol),Methyl 4-vinyl benzoate (116 mul, 0.75 mmol), toluene (1.5 ml) as a solvent, and a reaction at 130 oC for 60 hours. The reaction was terminated with water.Dilute hydrochloric acid (2 mol / L, 1 ml) was added for acidification, and the reaction product was extracted with ethyl acetate.Purification by column chromatography (using a mixed solvent of ethyl acetate / petroleum ether in a volume ratio of 1: 2 as a developing solvent), the yield was 78%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With tris(2,2'-bipyridyl)ruthenium dichloride; chloroform; [bis(acetoxy)iodo]benzene; In chloroform; at 20℃; for 12h;Irradiation; | General procedure: A 5 mL oven-dried reaction vessel equipped with a magnetic stirrer bar was charged with styrene (1a, 20.8 mg,0.20 mmol), Ru(bpy)3Cl2 (1.92 mg, 0.003 mmol, 1.5 mol%), PhI(OAc)2 (64.4 mg, 0.20 mmol, 1.0 equiv.) and CHCl3(2c, 2.0 mL). The reaction vessel was exposed to blue LED (450-455 nm, 3 W) at room temperature in air withstirring for 12 h. After completion of the reaction, the mixture was concentrated to yield the crude product, which wasfurther purified by flash chromatography (silica gel, petroleum ether/ethyl acetate = 10:1 to 5:1) to give the desiredproduct 5a. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With 2,6-di(t-butyl)-4-phenylphenol; caesium carbonate In dimethyl sulfoxide at 20℃; for 16h; Irradiation; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile; lithium chloride In dimethyl sulfoxide at 20℃; for 48h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile; lithium chloride In dimethyl sulfoxide at 20℃; for 48h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile; lithium chloride In dimethyl sulfoxide at 20℃; for 48h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile; lithium chloride In dimethyl sulfoxide at 20℃; for 48h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile; lithium chloride In dimethyl sulfoxide at 20℃; for 48h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
23% | With [RuCl2(N-heterocyclic carbene)(bis[2-(diphenylphosphino)ethyl]amine)]; potassium <i>tert</i>-butylate; hydrogen In tetrahydrofuran; 2-methyltetrahydrofuran at 45℃; for 2.5h; Autoclave; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86 % ee | With tert.-butylnitrite; tetrakis(actonitrile)copper(I) hexafluorophosphate; {3aS-[2(3'aR*,8'aS*),3aα,8aα]-2,2'-(cyclopropylidene)-bis{3a,8a-dihydro-8H-indeno[1,2-d]-oxazole} In acetonitrile at 25℃; for 48h; Sealed tube; Inert atmosphere; Overall yield = 82 percent; Overall yield = 66.4 mg; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | General procedure: A 15 mL Schlenk tube equipped with a stirrer bar was chargedwith CuCl (10 mol%), L7 (13 mol%), LiOMe (2.5 equiv), and theappropriate boronic ester 1 or 4 (0.375 mmol). The vessel wasthen evacuated and filled with Ar (three cycles). DMA (0.5 mL)and (Boc)2O (0.25 mmol) were added sequentially under Ar, andthe mixture was stirred at 30 for 6 h. MeI (5 equiv) was thenadded in air, and the mixture was stirred at 30 for additional2 h. The mixture was finally diluted with EtOAc and washedwith sat. aq NaCl (20 mL). The aqueous phase was furtherextracted with EtOAc (3 × 20 mL), and the combined organicphases were dried (Na2SO4) and concentrated. The residue waspurified by column chromatography [silica gel EtOAc-hexane(1:100 to 1:50)]. |
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