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Adrian O. Dukes ; Pathum M. Weerawarna ; Allison N. Devitt , et al. JOC,2024,89(12):9110-9117. DOI: 10.1021/acs.joc.4c00781 PubMed ID: 38857432
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Abstract: Inhibition of human ornithine aminotransferase interferes with glutamine and proline metabolism in hepatocellular carcinoma, depriving tumors of essential nutrients. A proposed mechanism-based inhibitor containing a bicyclo[3.1.1]heptanol warhead is reported herein. The proposed inactivation mechanism involves a novel α-iminol rearrangement. The synthesis of the proposed inhibitor features an asymmetric intramolecular Mannich reaction, utilizing a chiral sulfinamide. This study presents a novel approach toward the synthesis of functionalized bicyclo[3.1.1]heptanes and highlights an underutilized method to access enantiopure exocyclic amines.
Purchased from AmBeed: 23761-23-1 ; 1892-57-5 ; 505-23-7
CAS No. : | 23761-23-1 | MDL No. : | MFCD00100900 |
Formula : | C5H6O3 | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | IENOFRJPUPTEMI-UHFFFAOYSA-N |
M.W : | 114.10 | Pubchem ID : | 4913358 |
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: |
* 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 potassium osmate(VI) dihydrate; sodium periodate; In tetrahydrofuran; water; at 28℃;Industry scale; | To a solution of crude 3-methylenecyclobutane-carboxylic acid (280 g, 2.25 mol), water (5.5 L), THF (2.5 L) and potassium osmate dihydrate (2.11 g; 5.7 mmol), was charged portion-wise sodium periodate (1.1 kg, 5.14 mol) over a 1.5 h period. The inner temperature was kept below 28 C. To complete conversion additional potassium osmate dihydrate (0.5 g; 1,35 mmol) and sodium periodate (0.45 kg; 2.1 mol) were added. After 2 h stirring, the solids were removed via filtration and were subsequently washed with THF (1 L). The resulting filtrate was extracted with CH2C12 (7 x 1.5 L and 5 x 2 L) and EtOAc (9 2 L). The first 1.5 L CH2CI2 extract was set aside because of the relative large amount of by-product present. The other organic phases were combined and concentrated under reduced pressure. The solid material (approximately 140 g) was redissolved in CH2CI2 and was treated with charcoal (7 g). The charcoal was removed by filtration over Celite and the resulting filtrate was concentrated under reduced pressure, yielding a crystalline mass. This material was redissolved in toluene (150 mL) and to the solution was dosed hexane (1 0 mL). This yielded 52 g light yellowish/brown crystals, which darkened upon standing. Concentration of the mother liquor and recrystallization of the solid mass (70 g) from toluene (150 mL) yielded 48 g yellowish/brown material. The first CH2C12 extract which was set aside, was concentrated yielding 70 g of residue. To the residue CH2CI2 (30 mL) was added and the remaining solution was stored at -15C, which initiated crystallization. From this slurry, 55 g of dark grey/black needle-like crystals were recovered. All crystalline material was combined and was dissolved in EtOAc (750 mL) upon heating, charcoal (7.5 g) was added and the mixture was stirred for 1 h at ambient temperature. The charcoal was removed by filtration over Celite. Approximately 500 mL of EtOAc were removed under reduced pressure. At that point the product started to crystallize and severe foaming was observed. Hexane (500 mL) was added and the mixture was rotated on the rotary evaporator for 1 h. Filtration of the crystalline mass yielded pure product. Anal. Calcd. for C5H6O3: C, 52.63; H, 5.30. Found: C, 52.67; H, 5.31. MS (FIA/ES; negative ionization mode): m/e 430 [M-H] NMR (CDC13): δ 11.47 (br s, 1 H); 3.2-3.5 (m, 5 H). 13C NMR (CDC13): δ 203.1; 180.1; 51.5; 27.2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With dicyclohexyl-carbodiimide; In dichloromethane; at 20℃; | To a solution of commercially available 3-oxocyclobutanecarboxylic acid (11.4 g, 100 mmol) in anhydrous DCM (100 mL) was added DCC (31 g, 150 mmol) and 2 methylpropan-2-ol (8.9 g, 120 mmol), then the mixture was stirred at room temperature overnight. The mixture was quenched withaqueous H20, extracted with DCM, the organic layer was washed with brine, dried over anhydrous Na2SO4, filtered and concentrated in vacuo. The residue was purified by column to give reagent R-28b (15.1 g, 89percent yield). |
With dmap; dicyclohexyl-carbodiimide; In dichloromethane; at 20℃; for 20h; | Reference Example 4 Tert-butyl 3-oxocyclobutane carboxylate To dichloromethane solution (1.6 L) comprising 3-oxocyclobutane carboxylic acid obtained from Reference example 3, tert-butanol (429 g), 4-dimethylaminopyridine (283 g), dichloromethane solution (700 mL) comprising DCC (656 g) was added and the mixture was stirred at room temperature for twenty hours. Upon the completion of stirring, the reaction solution was filtered using Celite, and washed with 1N hydrochloric acid solution. The organic layer was washed with saturated sodium bicarbonate solution, and then dried over magnesium sulfate. Solids were removed, and the filtrate was dried under reduced pressure to obtain the title compound (530 g). 1H-NMR (CDCl3): 3.28 (4H, m), 1.48 (9H, s). | |
250 g | With dmap; dicyclohexyl-carbodiimide; In tetrahydrofuran; at 10 - 35℃; for 16.5h; | To a solution of 3-oxocyclobutanecarboxylic acid (250 g) in THF (1.5 L) were added tert-butanol (228 g) and 4-dimethylaminopyridine (148 g) at room temperature, and a solution of N,N'-dicyclohexylcarbodiimide (497 g) in THF (0.5 L) was added dropwise thereto over 30 min, and the reaction mixture was stirred at room temperature for 16 hr. The reaction mixture was filtered through Celite, and the filtrate was concentrated under reduced pressure. The residue was diluted with ethyl acetate, and the mixture was washed with 1M hydrochloric acid, saturated aqueous sodium hydrogencarbonate solution and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was diluted with petroleum ether, the mixture was filtered through Celite, and the filtrate was concentrated under reduced pressure to give the title compound (250 g). 1H NMR (500 MHz, CDCl3) delta 1.48 (9H, s), 3.12-3.14 (1H, m), 3.21-3.27 (2H, m), 3.33-3.35 (2H, m). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With potassium carbonate; In acetone; for 16h;Reflux; | A mixture of 3-oxocyclobutanecarboxylic acid (5 g, 44 mmol), potassium carbonate (12 g, 88 mmol) and benzyl bromide (11.2 g, 66 mmol) in acetone (50 mL) was refluxed for 16 hr. Solvent was then removed under reduced pressure and the residue was partitioned between ethyl acetate and water. Combined organic layers were dried over anhydrous MgSO/t, filtered and concentrated. The residue was purified with silica gel chromatography eluting with a gradient of 100% hexane to 96% hexane / EtOAc to give the desired compound (8.1 g, 90% yield). 1H NMR (400 MHz, CDC13): delta 7.45 - 7.27 (m, 5H), 5.19 (s, 2H), 3.55 - 3.36 (m, 2H), 3.33 - 3.11 (m, 3H). |
90% | With potassium carbonate; In [(2)H6]acetone; hexane; | Step A: Benzyl 3-oxocyclobutanecarboxylate A mixture of 3-oxocyclobutanecarboxylic acid (5 g, 44 mmol), potassium carbonate (12 g, 88 mmol) and benzyl bromide (11.2 g, 66 mmol) in acetone (50 mL) was refluxed for 16 hr. Solvent was then removed under reduced pressure and the residue was partitioned between ethyl acetate and water. Combined organic layers were dried over anhydrous MgSO4, filtered and concentrated. The residue was purified with silica gel chromatography eluting with a gradient of 100% hexane to 96% hexane/EtOAc to give the desired compound (8.1 g, 90% yield). 1H NMR (400 MHz, CDCl3): delta 7.45-7.27 (m, 5H), 5.19 (s, 2H), 3.55-3.36 (m, 2H), 3.33-3.11 (m, 3H). |
53% | With triethylamine; In tetrahydrofuran; at 20℃; for 2h; | Example 261 : 2-N-Methyl-6-[5-(3-phenoxycyclobutyl)-1 ,2,4-oxadiazol-3-yl]-2-N-phenyl- 1 ,3,5-triazine-2,4-diamineTriethylamine (2 mL, 14.04 mmol) and benzyl bromide (1.2 mL, 10.0 mmol) were added to a solution of 3-oxocyclobutane-1-carboxylic acid (1.0 g, 8.77 mmol) in THF (10 mL) and the mixture was stirred at room temperature for 2 h. EtOAc (10 mL) was added and the mixture was washed with water followed by 1 M hydrochloric acid and then brine. The organic layer was dried over sodium sulfate and concentrated under vacuum. The residue was purified by FCC, eluting with a gradient of 0-15% EtOAc in hexane to afford benzyl 3-oxocyclobutane-1-carboxylate (0.938 g, 53%). A portion of benzyl 3- oxocyclobutane-1-carboxylate (0.800 g, 3.92 mmol) was dissolved in a mixture of THF (2.5 mL) and water (2.5 mL) and cooled to 0 C. Sodium borohydride (0.051 g, 1.96 mmol) was added and the mixture was stirred at room temperature for 1 h. The mixture was concentrated under vacuum and EtOAc (10 mL) was added. This was washed with water and then brine and the organic layer was then dried over sodium sulfate and concentrated. The residue was purified by FCC, eluting with a gradient of 0-10% EtOAc in hexane to afford benzyl 3-hydroxycyclobutane-1-carboxylate (0.715 g, 88%). A portion of benzyl 3-hydroxycyclobutane-1-carboxylate (0.400 g, 1.94 mmol) was dissolved in THF (10 mL) and phenol (0.547 g, 5.83 mmol) and triphenylphosphine (0.662 g, 2.52 mmol) were added. Diethyl azodicarboxylate (0.4 mL, 2.52 mmol) was added gradually and the mixture was stirred at room temperature for 24 h. The mixture was evaporated and then extracted with EtOAc (3 x 10 mL). The organic layer was washed with brine and concentrated under vacuum. The residue was purified by FCC, eluting with a gradient of0- 15% EtOAc in hexane to afford benzyl 3-phenoxycyclobutane-1-carboxylate (0.450 g, 82%). A portion of benzyl 3-phenoxycyclobutane-1-carboxylate (0.400 g, 1.42 mmol) was dissolved in EtOH (10 mL) and 10% palladium on carbon (0.010 g) was added. The mixture was stirred under an atmosphere of hydrogen at room temperature for 2 h. The mixture was filtered and the filtrate was evaporated. The residue was purified by FCC, eluting with a gradient of 0-10% EtOAc in hexane to afford 3-phenoxycyclobutane-1- carboxylic acid (0.245 g, 95%). 2-N-Methyl-6-[5-(3-phenoxycyclobutyl)-1 ,2,4-oxadiazol-3- yl]-2-N-phenyl-1 ,3,5-triazine-2,4-diamine was then prepared from 3-phenoxycyclobutane-1- carboxylic acid (0.190 g, 0.985 mmol) and 4-amino-N-hydroxy-6- [methyl(phenyl)amino]-1 ,3,5-triazine-2-carboximidamide (prepared in an analogous manner to Intermediate 1 , 0.150 g, 0.579 mmol) according to the method described for Example 209. The residue was purified by FCC, eluting with 10% MeOH in hexane to afford the title compound as a mixture of isomers (0.095 g, 42%). |
41.9% | With potassium carbonate; In acetone; for 10h;Reflux; | 3-Oxocyclobutanecarboxylic acid(3.0 g, 26.3 mmol), benzyl bromide(6.7 g, 39.4 mmol) and potassium carbonate(7.3 g, 52.6 mmol) was dissolved in acetone(30 mL), and then heated to reflux for 10 hours. After TLC showed that the reaction was completed, the reaction mixture was concentrated under reduce pressure to remove the solvent, added water (20 mL), and extracted with ethyl acetate (150 mL*2). The combined organic phase was washed with saturated salt water(50 mL), dried with anhydrous sodium sulfate, filtered and concentrated under vacuum. The residue was purified through silica gel column chromatography (petroleum ether/ethyl acetate=10:1) to give benzyl 3-oxocyclobutane-carboxylate (2.5 g, 41.9% yield) as a colorless liquid. MS (ESI) Calcd. for C12H12O3 [M+H]+ 205, Found 205. |
36.7% | With caesium carbonate; In acetonitrile; at 20℃; for 20h;Inert atmosphere; | To a mixture of commercially available 3-oxocyclobutanecarboxylic acid (13.50 g,118.32 mmol) and Cs2003 (46.26 g, 141.98 mmol) in CH3CN (120 mL), was added bromomethylbenzene (21 .25 g, 124.24 mmol) in one portion at r.t. under N2. The mixture was stirred at r.t. for 20 hours. LCMS and TLC showed the reaction was completed. The residue was poured into water and stirred for 20 mm. The aqueous phase was extracted with EtOAc (120 mL). Thecombined organic phase was washed with saturated brine (140 mL), dried with anhydrous Na2SO4, filtered and concentrated in vacuum. The residue was purified by silica gel chromatography to afford reagent KR-Si (8.86 g, 36.7%). |
With triethylamine; In tetrahydrofuran; at 20℃; for 2h; | Triethylamine (2.0 mL) and benzyl bromide (1.2 mL) were added to a solution of 3-oxocyclobutanecarboxylic acid (J. Org. Chem., vol. 53, pp. 3841-3843 (1981)) (995 mg) in tetrahydrofuran (5.0 mL), and the mixture was stirred at room temperature for 2 hours. The reaction mixture was diluted with ethyl acetate, and was sequentially washed with 1N aqueous HCl, saturated aqueous sodium hydrogencarbonate, and saturated brine, followed by drying over sodium sulfate anhydrate. The solvent was distilled away under reduced pressure, and the residue was purified by silica gel column chromatography (ethyl acetate : hexane = 1:6), to thereby give the title compound (886 mg).1H-NMR(CDCl3) delta:3.22-3.33(3H, m), 3.37-3.48(2H, m), 5.19(2H, s), 7.31-7.42(5H, m).MS(FAB)m/z:205(M+H+). | |
With sodium hydrogencarbonate; triethylamine; In tetrahydrofuran; | REFERENTIAL EXAMPLE 150 Benzyl 3-oxocyclobutanecarboxylate: Triethylamine (2.0 ml) and benzyl bromide (1.2 ml) were added to a solution of 3-oxocyclobutanecarboxylic acid (J. Org. Chem., Vol. 53, pp. 3841-3843, 1981) (995 mg) in tetrahydrofuran (5.0 ml), and the mixture was stirred at room temperature for 2 hours. The reaction mixture was diluted with ethyl acetate, and washed successively with 1N hydrochloric acid, a saturated aqueous solution of sodium hydrogencarbonate and saturated saline and dried over anhydrous sodium sulfate. The solvent was then distilled off under reduced pressure, and the resultant residue was purified by column chromatography on silica gel (ethyl acetate:hexane=1:6) to obtain the title compound (886 mg). 1H-NMR (CDCl3) delta: 3.22-3.33(3H,m), 3.37-3.48(2H,m), 5.19(2H,s), 7.31-7.42(5H,m). | |
Step A:3-Oxocyclobutanecarboxylic acid (2-A) (1.0 g, 10.0 mmol) was dissolved in anhydrous ethanol (25 ml), and cesium carbonate (1.66 g, 5.1 mmol) was added. After stirring at room temperature under nitrogen for 4 hours, the reaction mixture was concentrated. The residue was redissolved in anhydrous acetonitrile (50 ml) and treated with benzyl bromide (1.2 ml, 10.0 ml). The mixture was allowed to stir at room temperature under nitrogen for 12 hours. Solvent was then removed under reduced pressure and the residue was partitioned between ethyl acetate and water. The crude product was purified with silica gel chromatography eluting with a gradient of 100% hexane to 96% hexane/ethyl acetate to give 2-B. | ||
With triethylamine; In tetrahydrofuran; at 20℃; for 2h; | [Referential Example 150] benzyl 3-oxocyclobutanecarboxylate: triethylamine (2.0 ml) and benzyl bromide (1.2 ml) were added to a solution of 3-oxocyclobutanecarboxylic acid (J. Org. Chem., Vol. 53, pp. 3841-3843, 1981) (995 mg) in tetrahydrofuran (5.0 ml), and the mixture was stirred at room temperature for 2 hours.. The reaction mixture was diluted with ethyl acetate, and washed successively with 1N hydrochloric acid, a saturated aqueous solution of sodium hydrogencarbonate and saturated saline and dried over anhydrous sodium sulfate.. The solvent was then distilled off under reduced pressure, and the resultant residue was purified by column chromatography on silica gel (ethyl acetate:hexane = 1:6) to obtain the title compound (886 mg).1H-NMR (CDCl3) delta: 3.22-3.33(3H,m), 3.37-3.48(2H,m), 5.19(2H,s), 7.31-7.42(5H,m). MS (FAB) m/z: 205(M+H+). | |
With potassium carbonate; In acetonitrile; at 20℃; for 24h; | BnBr was added to the mixture of compound 1 and K2CO3 in acetonitrile 150 mL. The mixture was stirred at room temperature over 24 h and the solid was filtered. The solvent was removed and the residue was purified by column chromatography to give compound 2. | |
With potassium carbonate; In acetonitrile; at 20℃; for 24h; | Step 1: benzyl 3-oxocyclobutanecarboxylate (2) Referring to Scheme 6A, BnBr was added to the mixture of compound 1 and K2CO3 in acetonitrile 150 mL. The mixture was stirred at room temperature over 24 h and the solid was filtered. The solvent was removed and the residue was purified by column chromatography to give compound 2. | |
With potassium carbonate; In [(2)H6]acetone; hexane; | Step A: Benzyl 3-oxocyclobutanecarboxylate A mixture of 3-oxocyclobutanecarboxylic acid (5 g, 44 mmol), potassium carbonate (12 g, 88 mmol) and benzyl bromide (11.2 g, 66 mmol) in acetone (50 mL) was refluxed for 16 h. The solvent was then removed under reduced pressure and the residue was partitioned between ethyl acetate and water. Combined organic layers were dried over anhydrous MgSO4, filtered and concentrated. The residue was purified with silica gel chromatography eluting with a gradient of 100% hexane to 96% hexane/EtOAc to give the desired compound. 1H NMR (400 MHz, CDCl3): delta 7.45-7.27 (m, 5H), 5.19 (s, 2H), 3.55-3.36 (m, 2H), 3.33-3.11 (m, 3H). | |
With potassium carbonate; In acetone; for 16h;Reflux; | Method Step A: Benzyl 3-oxocyclobutanecarboxylate. A mixture of 3-oxocyclobutanecarboxylic acid (5 g, 44 mmol), potassium carbonate (12 g, 88 mmol) and benzyl bromide (1 1.2 g, 66 mmol) in acetone (50 mL) was refluxed for 16 h. The solvent was then removed under reduced pressure and the residue was partitioned between ethyl acetate and water. Combined organic layers were dried over anhydrous MgS04, filtered and concentrated. The residue was purified with silica gel chromatography eluting with a gradient of 100% hexane to 96% hexane / EtOAc to give the desired compound. FontWeight="Bold" FontSize="10" H NMR (400 MHz, CDC13): delta 7.45 - 7.27 (m, 5H), 5.19 (s, 2H), 3.55 - 3.36 (m, 2H), 3.33 - 3.11 (m, 3H). | |
To a solution of commercially available 3-oxocyclobutanecarboxylic acid (14.9 g) in DMF (210 mL) were added potassium carbonate (27.07 g) and benzyl bromide (18.6 mL), and the mixture was stirred at room temperature for 2 hr. To the reaction mixture was added acetic acid (22.4 mL) over 12 min, and the mixture was stirred at room temperature for 10 min. Water (350 mL) was added, and the mixture was extracted 3 times with ethyl acetate. The organic layer was washed 4 times with saturated brine, dried over magnesium sulfate and concentrated. [1411] Toluene was added and the mixture was concentrated to give a crude product of compound 3-1. The obtained crude product of compound 3-1 was directly used in the next step. | ||
With potassium carbonate; In acetone; for 16h;Reflux; | A mixture of 3-oxocyclobutanecarboxylic acid (5g, 44 mmol), potassium carbonate (12 g, 88 mmol) and benzyl bromide (11.2 g, 66 mmol) in acetone (50 mL) was refluxed for 16 h. The solvent was then removed under reduced pressure and the residue was partitioned between ethyl acetate and water. Combined organic layers were driedover anhydrous MgSO4, filtered and concentrated. The residue was purified with silica gel chromatography eluting with a gradient of 100% hexane to 96% hexane EtOAc to givethedesired compound. ?H NMR (400 MHz, CDC13): 7.45 - 7.27 (m, 511), 5.19 (s, 211), 3.55-3.36 (m, 211), 3.33 -3.11 (m, 311). | |
With potassium carbonate; In acetone; for 16h;Reflux; | Step A: Benzyl 3-oxocyclobutanecarboxylate. A mixture of 3-oxocycIobutanecarboxylic acid (5 g, 44 mmol), potassium carbonate ( 12 g, 88 mmol) and benzyl bromide (1 1.2 g, 66 mmol) in acetone (50 mL) was refluxed for 1 h. The solvent was then removed under reduced pressure and the residue was partitioned between ethyl acetate and water. Combined organic layers were dried over anhydrous MgSC , filtered and concentrated. The residue was purified with silica gel chromatography eluting with a gradient of 100% hexane to 96% hexane / EtOAc to give the desired compound. NMR (400 MHz, CDC13): delta 7.45 - 7.27 (m, 5H), 5.19 (s, 2H), 3.55 - 3.36 (m, 2H), 3.33 - 3.1 1 (m, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Step 1: 3-tert-Butoxycarbonylmethylene-cyclobutanecarboxylic acid A mixture of 1.2 g of cyclobutanone-3-carboxylic acid (Pigou, P. E.; Shiesser, C. H.; J. Org. Chem.53, 3841-3, 1988), 2.8 g of tert-butyl-dimethyl phosphono-acetate, 1.0 g of lithium hydroxide which had been dried at 120° C. for 30 min under vacuum, 6 g of activated 4A (heated in microwave oven then dried under vacuum for 1 h) molecular sieve dust and 50 mL of THF was heated to reflux under nitrogen for 24 h, cooled, diluted with 100 mL of ethyl acetate and 100 mL of 1N HCl and filtered through diatomaceous earth. The layers were separated and the aqueous layer extracted 4*mL of ethyl acetate. The combined organic extracts were diluted with 50 mL of toluene and concentrated under reduced pressure. Drying under vacuum overnight gave 2 g of product as a white crystalline solid: 1H NMR (400 MHz, CDCl3) 5.5 (s, 1H), 3.9-3.0 (complex m, 4H), 1.42 (s, 9H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With toluene-4-sulfonic acid; In toluene; for 3h;Heating; | To 3-oxocyclobutanecarboxylic acid (10 g, 87,6 mmol) in dry toluene (100 mL) was added benzyl alcohol (9,1 mL, 87,6 mmol) and p-toluenesulphonic acid (0,4 g, 2,1 mmol). The reaction was heated under Dean-Stark conditions for 3 h. The reaction was concentrated to dryness in vacuo to afford the crude product. Purification using silica chromatography (ethyl acetate/hexane, 0-100% gradient) gave benzyl 3-oxocyclobutanecarboxylate (6) (16 g; 89%) as a colourless oil.1H NMR CDCl3: delta ppm 7.30 (s, 5H), 5.10 (s, 2H), 3.43-3.29 (m, 2H), 3.28-3.13 (m, 3H). |
84% | With 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride;dmap; In dichloromethane; at 20℃; for 18h; | Intermediate 1 (3. 5g, 30.7 mmol), benzyl alcohol (3.17 ml, 30.7 mmol), DMAP (375mg, 3.07 mmol), EDC (8.8g, 46.0 mmol) and DCM (100 ml) were mixed together and stirred at room temperature for 18 hours. The reaction mixture was washed with water (3x). The combined aqueous layer was extracted with DCM. The combined organic layer was washed with brine, dried over anhydrous MGS04, and concentrated IN VACUO. Crude product was purified by MPLC (30: 70, ethyl acetate: hexanes) to yield Intermediate 3 (5.25g, 84.0%). NMR (400 MHz, CDC13) 8 7.39 (m, 4H), 5.21 (s, 2H), 3.49-3. 41 (m, 2H), 3.36-3. 28 (m, 3H). |
66% | Slowly add carbonyldiimidazole (42.6 g, 263 mmol) to a solution of 3-oxo- cyclopropane carboxylic acid (25.0 g, 219 mmol) in DCM (500 mL), stir at RT for 2 h, add benzyl alcohol (24.17 g, 223 mmol) and stir at RT for 16 h. Add water, extract with DCM (2x), wash the combined organics with brine, dry over Na2S04, concentrate to dryness and purify by silica gel chromatography (EtOAc/Hex) to afford the title compound (29.5 g, 66%) as a colorless syrup. 1H NMR (400 MHz, DMSO-d6): delta 7.38- 7.35 (m, 5 H); 5.14 (s, 2 H); 3.62 (m, 5 H); MS (ESI) m/z: 227.1 (M+Na+). |
66% | Example 1 Carbonyldiimidazole (42.6 g, 263 mmol) was slowly added to a solution of 3-oxo-cyclopropane carboxylic acid (25.0 g, 219 mmol) in DCM (500 mL), stirred at RT for 2 h, treated with benzyl alcohol (24.17 g, 223 mmol) and stirred at RT for 16 h. The mixture was diluted with water, extracted with DCM (2*) and the combined organics were washed with brine, dried over Na2SO4, concentrated to dryness and purified by silica gel chromatography (EtOAc/Hex) to afford benzyl 3-oxocyclobutanecarboxylate (29.5 g, 66%) as a colorless syrup. 1H NMR (400 MHz, DMSO-d6): delta 7.38-7.35 (m, 5H); 5.14 (s, 2H); 3.62 (m, 5H); MS (ESI) m/z: 227.1 (M+Na+). | |
3.15 g | With 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane; at 20℃; for 18h; | A mixture of 3-oxocyclobutanecarboxylic acid (2.15 g, 18.84 mmol), benzyl alcohol (2.145 mL, 20.73 mmol) and Nl-((ethylimino)methylene)-N3,N3- dimethylpropane- 1,3 -diamine, HC1 (5.42 g, 28.3 mmol) in DCM (100 mL) was stirred at room temperature for 18 hours. The reaction mixture was washed with water (3x) and the combined aqueous layers were extracted with DCM. The combined organic layesr were washed with brine, dried over anhydrous MgS04, and concentrated in vacuo. Crude product was purified by FCC (0% to 35% EtOAc- Hexanes) to yield the desired product Cap W-25/Cap W-26 Step A (3.15 g) as a colorless oil.1HNMR (400 MHz, CDC13) delta 7.39 (m, 5H), 5.21 (s, 2H), 3.49-3. 41 (m, 2H), 3.36-3. 28 (m, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sulfuric acid; magnesium sulfate; In dichloromethane; at 20℃; for 60h; | A Concentrated sulfuric acid (5 ML, 90 mmol) was added to a vigorously stirred suspension of anhydrous MGS04 (42 g, 350 mmol) in DCM (250 mL). The mixture was stirred for 15 minutes before Intermediate 1 (10 g, 88 mmol) was added followed by tert-butanol (42.5 ML, 438 mmol). The reaction flask was stoppered tightly and stirred at room temperature for 60 hours. Saturated NaHC03 solution was added and the resulting mixture was stirred until the reaction mixture became clear as all MGS04 dissolved. The organic layer was separated and washed with brine, dried over anhydrous MGS04, and concentrated in vacuo. The crude product was used in next step. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | A 2.7 M solution of n-BuLi in heptane (3.6 mL, 9.6 mmol) was added for 5 min to a solution of intermediate 4, (2i?)-l-(4-bromo-2-chlorobenzyl)-2- methylpyrrolidine. (2.52 g, 8.8 mmol) in absolute THF (20 ml) in a flow of argon at - 78 to -80 0C. The reaction mixture was stirred at -78 to -80 0C for 15 min. Then a solution of 3-oxocyclobutanecarboxylic acid (500 mg, 4.4 mmol) in absolute THF (4 mL) was added drop wise over 5 min at -80 0C. The mixture was warmed to 0 0C for 1 h and evaporated to dryness. The residue was dissolved in DMF (10 mL), Intermediate 5, pyrrolidine HCl (520 mg, 4.8 mmol) was added. Then BOP (2.2 g, 4.8 mmol) was added in portions under cooling in an ice bath for 16 h at room temperature. The disappearance of the starting hydroxy acid was monitored by LC/MS. The reaction mass was evaporated to dryness under 1 mmHg. Water (100 mL), EtOAc (50 mL), and a saturated solution OfK2CO3 (to pH 10) were added. The layers were separated, and the aqueous one was subjected to extraction with EtOAc (2 x 50 mL). The combined organic layer was washed with water (50 mL), brine, dried with Na2SO4, and evaporated. The residue was purified by chromatography (60 mL of silica gel 63/100 μm, hexane/CHCl3 20:80 → 0:100, then CHCl3MeOH <n="33"/>100:0 → 90:10). The product-containing fraction were collected and concentrated to give the title compound (1.03 g, 63%). LC/MS data: 377.2 and 379.2 (M)+ (calculated for C2iH29ClN2O2 376.93). IH NMR data (DMSO-d6): δ 7.51 (s, IH, Ar- H); 7.42-7.49 (m, 2H, Ar-H), 5.75 (s, IH, OH); 3.96 (d, IH, J=13.7 Hz)5 3.25-3.35 (m, ?H+H20); 2.78-2.90 (m, 2H); 2.53-2.60 (m, 2H); 2.43-2.52 (m, 7H+DMSO); 2.06-2.16 (m, IH); 1.88-1.97 (m, IH); 1.80-1.87 (m, 2H); 1.72-1.79 (m, 2H); 1.57- 1.67 (m, 2H); 1.29-1.40 (m, IH); 1.11 (d, 3H, J=5.8 Hz, CH3) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With dmap; triethylamine; In dichloromethane; at 0℃; for 1h; | To a mixture of 3-oxocyclobutanecarboxylic acid (175 mmol) and TEA (20.4 g, 202 mmol) in DCM (300 ml) at 0C added benzyl chloroformate (3 1.4 g, 184 mmol) slowly. After the addition, DMAP (2.14 g, 17.53 mmol) added. The reaction mixture stirred at 0C for one hour. Then concentrated under vacuum to get 35.8 g (100%) of benzyl 3-oxocyclobutanecarboxylate as colorless oil. LC-MS (ES, m/z) C12H12O3 : 204; Found: 205 [M+H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
2.7 g | Example 113 4- ( (4-Fluorobenzyl) oxy) -1- ( l-methyl-2- (3-oxocyclobutyl) -1H- benzimidazol-6-yl) pyridin-2 (1H) -one A) N- ( 4-Bromo-2- (methylamino) henyl) -3- oxocyclobutanecarboxamide To a stirred solution of 3-oxocyclobutanecarboxylic acid (1.1 g) in DMF (50 ml) were added HATU (5.7 g) and N,N- diisopropylethylamine (4.2 ml) at 0C. The mixture was allowed to warm to room temperature and stirred for 30 min. A solution of 4-bromo-N2-methylbenzene-l, 2-diamine (2.0 g) in DMF (2 ml) was added, and the resultant mixture was stirred at the same temperature for 18 h. The mixture was then concentrated in vacuo, and the residue was diluted with DCM (200 ml) and washed with saturated NH4C1 (100 ml), saturated NaHC03. (60 ml), water (100 ml) and brine (100 ml) . The DCM layer was then dried over Na2S04 and concentrated in vacuo. The residue was purified by silica gel column chromatography (hexane/EtOAc) to give the title compound (2.7 g) as an off-white solid. MS (ESI+) : [M+H]+ 297.2. |
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