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[ CAS No. 119479-32-2 ] Boc-DL-Allyl-Gly-OH

Cat. No.: A502111
Chemical Structure| 119479-32-2
Chemical Structure| 119479-32-2
Structure of 119479-32-2 * Storage: Keep in dark place,Sealed in dry,2-8°C
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98% 250mg $21.00 Inquiry Inquiry
98% 1g $45.00 Inquiry Inquiry
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98% 25g $670.00 Inquiry Inquiry

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Product Details of [ 119479-32-2 ]

CAS No. :119479-32-2 MDL No. :MFCD02682445
Formula : C10H17NO4 Boiling Point : -
Linear Structure Formula :CO2HCHNHCO2C4H9C3H5 InChI Key :BUPDPLXLAKNJMI-UHFFFAOYSA-N
M.W : 215.25 Pubchem ID :5166119
Synonyms :
Chemical Name :2-((tert-Butoxycarbonyl)amino)pent-4-enoic acid

Safety of [ 119479-32-2 ]

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:

Application In Synthesis of [ 119479-32-2 ]

* 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.

  • Downstream synthetic route of [ 119479-32-2 ]

[ 119479-32-2 ] Synthesis Path-Downstream   1~21

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YieldReaction ConditionsOperation in experiment
94% With sodium hydroxide; In 1,4-dioxane; water; at 0℃; for 16h; A solution of di-tert-butyl dicarbonate (11.4 g, 52.1 mmol) in 1,4-dioxane (15 mL) was slowly added to a second solution of 2-amino-5-pentenoic acid (5 g, 43.4 mmol) in 1 N NAOH (55 mL) at 0 C. After stirring for 16h, the solution was acidified with 5% HC1 to pH 2, and the resulting mixture was extracted with ethyl acetate (3 x 80 mL). The combined organic layers were dried OVER MGS04 and concentrated. The resulting residue was dissolved in DMF (50 mL) and treated with K2CO3 (7 g, 51 MMOL). After stirring for 15 min, the solution was cooled to 0 C and treated with iodomethane (3.4 mL, 51 mmol). After the addition was complete, the reaction mixture was stirred at room temperature for another 4 h, filtered and the resulting solid was washed with ethyl acetate (200 mL). The filtrate was washed successively with 5% aq HC1, sat. aq NaCl, dried over MGS04 and concented. Purification by flash column chromatography (5% ethyl acetate in heptane) provided 2-tert-Butoxycarbonylamino-5-pentenoic acid methyl ester (9.03 g, 94%) as an oil. 1H NMR (CDC13), 5.73 (m, 1 H), 5.12 (m, 1 H), 5.03 (m, 1 H), 4.38 (dd, J = 6, 12 Hz, 1 H), 3.74 (s, 3 H), 2.51 (m, 2 H), 1.46 (s, 9 H).
93% rac. )-2-tert-Butoxycarbonylamiiio-pent-4-enoic acid (A); A solution of DL-allylglycine (20.2 g; 175mmol) in THF/H2O (670/670 ml) was cooled to 0 0C. NaHCO3 (44.11g; 525mmol) was added portionwise and BoC2O (68.8g; 315mmol) was added also portionwise. The reaction mixture was stirred at 0 C under N2 for 5 min, then at rt overnight. The pH of the milky mixture was adjusted to 4 by carefully addition of saturated citric acid at 0C, and the mixture was extracted with EtOAc. The combined org. layers were washed with brine, dried over MgSO4, filtered, and concentrated under reduced pressure. The title compound was isolated as a white solid (35.1 g, 93%).
58% A mixture of 2-aminopent-4-enoic acid (230mg, 2mmol), water (3mL) and tert-butanol (1mL) was treated with NaOH (88mg, 2.2mmol) and stirred until a clear solution was obtained (2-5min). Then Boc-anhydride (654mg, 3mmol) in tert-butanol (1.3mL) was added and stirred at r.t. overnight. The reaction mixture was extracted with diethyl ether (2×25mL). The combined ethereal layer was extracted with saturated Na2CO3 (2×25mL) and the combined aqueous layer was acidified with conc. HCl to pH 1. The aqueous layer was extracted with diethyl ether (3×25mL). The combined organic extracts were washed with brine (25mL), dried (MgSO4) and the solvent was evaporated to give a light brownish oil. Yield: 250mg (58%). 1H NMR (CDCl3) δ 1.42 (s, 9H, CH3), 2.57 (br m, 2H, H-3), 4.22 (br m, 0.25 H, H-2), 4.39 (br m, 0.75 H, H-2), 5.10 (br m, 0.75 H, NH), 5.13 (s, 1H, H-5cis), 5.18 (d, 3J=9Hz, H-5trans), 5.74 (m, 1H, H-4), 6.11 (br m, 0.25 H, NH), 8.24 (br s, 1H, CO2H). 13C NMR (CDCl3) δ 28.3 (q, CH3), 36.4 (t, C-3), 52.8 (d, C-2), 80.3 (s, O-C), 119.3 (t, C-5), 132.2 (d, C-4), 155.5 (s, Boc), 176.2 (s, C-1).
With sodium hydroxide; potassium hydrogensulfate; In 1,4-dioxane; ethyl acetate; Step 1: N-Boc-L-2-amino-4-pentenoic acid To a solution of L-2-amino-4-pentenoic acid (1.15 g, 10.0 mmol) in a mixture of dioxane (10 mL) and 1N NaOH (10 mL) was stirred in an ice bath. Di-tert-butyl pyrocarbonate (2.4 g, 11.0 mmol) was added and stirring was continued for 1 h. The solution was concentrated to 10 mL and 30 mL of EtOAc was added. The solution was made acidic (pH = 3) by the addition of solid KHSO4. The aqueous phase was extracted with EtOAc (2 x 10 mL) and dried over MgSO4. Evaporation of the solvent afforded the N-Boc protected amino acid as a white solid. 1H NMR (CDCl3) δ 5.75 (m, 1H), 5.20 (m, 2H), 5.05 (d, J=5.0 Hz, 1H), 4.40 (d, J=5.0 Hz, 1H), 4.57 (m, 2H), 1.47 (s, 9H).
Reference Example 34 2-Amino-5-[4-(methyl-pyrimidin-2-ylamino)phenyl]pent-4-enoic acid methyl ester [Show Image] (1) Allylglycine (1.82 g) was dissolved in 1N aqueous sodium hydroxide solution (60 ml), and di-tert-butyl dicarbonate (4.15 g) was added thereto, followed by stirring the resulting mixture at room temperature for 11 hours. Di-tert-butyl dicarbonate (4.15 g) was further added to the reaction solution and the resulting mixture was stirred at room temperature overnight. After adding water to the reaction solution and washing it with ether, the solution was acidified with 3N hydrochloric acid. The solution was extracted twice with ethyl acetate. Organic layers were washed with saturated brine and dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the filtrate was concentrated. The residue was recrystallized from hexane/ethyl acetate mixed solvent to obtain N-Boc-allylglycine (3.09 g).
With sodium hydroxide; In water; at 20℃; Reference Example 34 2-Amino-5-[4-(methyl-pyrimidin-2-ylamino)phenyl]pent-4-enoic acid methyl ester [Show Image] (1) Allylglycine (1.82 g) was dissolved in 1N aqueous sodium hydroxide solution (60 ml), and di-tert-butyl dicarbonate (4.15 g) was added thereto, followed by stirring the resulting mixture at room temperature for 11 hours. Di-tert-butyl dicarbonate (4.15 g) was further added to the reaction solution and the resulting mixture was stirred at room temperature overnight. After adding water to the reaction solution and washing it with ether, the solution was acidified with 3N hydrochloric acid. The solution was extracted twice with ethyl acetate. Organic layers were washed with saturated brine and dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the filtrate was concentrated. The residue was recrystallized from hexane/ethyl acetate mixed solvent to obtain N-Boc-allylglycine (3.09 g).
Allylglycine (1.82 g) was dissolved in 1N aqueous sodium hydroxide solution (60 ml), and di-tert-butyl dicarbonate (4.15 g) was added thereto, followed by stirring the resulting mixture at room temperature for 11 hours. Di-tert-butyl dicarbonate (4.15 g) was further added to the reaction solution and the resulting mixture was stirred at room temperature overnight. After adding water to the reaction solution and washing it with ether, the solution was acidified with 3N hydrochloric acid. The solution was extracted twice with ethyl acetate. Organic layers were washed with saturated brine and dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the filtrate was concentrated. The residue was recrystallized from hexane/ethyl acetate mixed solvent to obtain N-Boc-allylglycine (3.09 g).

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YieldReaction ConditionsOperation in experiment
70% With benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate; N-ethyl-N,N-diisopropylamine; In N,N-dimethyl-formamide; at 20℃; for 3.16667h; (rαc.)-[(2-terMButoxycarbonylamino-pent-4-enoyl)methylamino]acetic acid methyl ester (B); PyBop (24.06g; 46.3 mmol) was added to a sol. of compound B (9.00 g; 42.04mmol) in DMF (200 mL) nnder N2 at rt. The sol. was stirred for 10 min at rt, and sarcosine methylester hydrochloride (6.46g; 46.3 mmol) and DIPEA (23.8 mL; 139 mmol) were added dropwise. The mixture was stirred at rt for 3 hours. EtOAc (400 mL) was added and the resulting organic phase was washed with brine (3x). The combined org. layers were dried over MgSO4, filtered, and the solvents were removed under reduced pressure. The crude product was diluted again in EtOAc (150 mL) and the mixture was washed with water (2x). The combined org. layers were dried over MgSO4, filtered, and the solvents were removed under reduced pressure. Purification of the residue by FC (CH2Cl2/Me0H 50:1) yielded the title compound (8.82 g, 70%)
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  • [ 78-84-2 ]
  • cinnamyl amine resin [ No CAS ]
  • [1-(1-benzylcarbamoyl-2-methyl-propyl)-2-oxo-2,3,4,7-tetrahydro-1<i>H</i>-azepin-3-yl]-carbamic acid <i>tert</i>-butyl ester [ No CAS ]
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  • cinnamyl amine resin [ No CAS ]
  • [1-(benzylcarbamoyl-phenyl-methyl)-2-oxo-2,3,4,7-tetrahydro-1<i>H</i>-azepin-3-yl]-carbamic acid <i>tert</i>-butyl ester [ No CAS ]
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  • cinnamyl amine resin [ No CAS ]
  • [1-(1-benzylcarbamoyl-3-phenyl-propyl)-2-oxo-2,3,4,7-tetrahydro-1<i>H</i>-azepin-3-yl]-carbamic acid <i>tert</i>-butyl ester [ No CAS ]
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YieldReaction ConditionsOperation in experiment
5.18 g With N-ethyl-N,N-diisopropylamine; N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate; In dichloromethane; at 21 - 25℃; for 18h;Inert atmosphere; [0213] Into a 250 mL round-bottom flask equipped with a magnetic stir bar and under N2 was added 2-((tert-butoxycarbonyl)amino)pent-4-enoic acid (5.00 g, 23.2 mmol, 1.0 equiv), N,O-dimethylhydroxylamine hydrochloride (2.49 g, 25.5 mmol, 1.1 equiv), HATU (10.6 g, 27.8 mmol, 1.2 equiv) and CH2Cl2 (50 mL). The reaction mixture was treated with EtN(iPr)2 (8.1 mL, 46.4 mmol, 2 equiv) and the suspension was stirred at room temperature for 18 h overnight. The reaction mixture was quenched with 1 M aqueous HCl solution (50 mL), and poured into a 250 mL separatory funnel containing water (50 mL). The mixture was extracted with CH2Cl2 (3 × 50 mL) and the combined organic layers were washed with brine (50 mL), dried over MgSO4, filtered and concentrated under reduced pressure. Purification by recrystallization from hot Et2O afforded a slight yellow solid, which was dried under vacuum (5.18 g).
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  • [benzyl-(2-<i>tert</i>-butoxycarbonylamino-pent-4-enoyl)-amino]-acetic acid methyl ester [ No CAS ]
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  • [ 74-88-4 ]
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YieldReaction ConditionsOperation in experiment
94% A solution of di-tert-butyl dicarbonate (11.4 g, 52.1 mmol) in 1,4-dioxane (15 mL) was slowly added to a second solution of 2-amino-5-pentenoic acid (5 g, 43.4 mmol) in 1 N NAOH (55 mL) at 0 C. After stirring for 16h, the solution was acidified with 5% HC1 to pH 2, and the resulting mixture was extracted with ethyl acetate (3 x 80 mL). The combined organic layers were dried OVER MGS04 and concentrated. The resulting residue was dissolved in DMF (50 mL) and treated with K2CO3 (7 g, 51 MMOL). After stirring for 15 min, the solution was cooled to 0 C and treated with iodomethane (3.4 mL, 51 mmol). After the addition was complete, the reaction mixture was stirred at room temperature for another 4 h, filtered and the resulting solid was washed with ethyl acetate (200 mL). The filtrate was washed successively with 5% aq HC1, sat. aq NaCl, dried over MGS04 and concented. Purification by flash column chromatography (5% ethyl acetate in heptane) provided 2-tert-Butoxycarbonylamino-5-pentenoic acid methyl ester (9.03 g, 94%) as an oil. 1H NMR (CDC13), 5.73 (m, 1 H), 5.12 (m, 1 H), 5.03 (m, 1 H), 4.38 (dd, J = 6, 12 Hz, 1 H), 3.74 (s, 3 H), 2.51 (m, 2 H), 1.46 (s, 9 H).
79% With potassium carbonate; In N,N-dimethyl-formamide; at 0 - 20℃; for 7h; Methyl N-Boc-2-aminopent-4-enoic acid (250mg, 1.163mmol) was dissolved in dry DMF (3mL) and K2CO3 (241mg, 1.744mmol) was added. The suspension was cooled to 0C and methyl iodide (330mg, 2.326mmol) was added slowly with stirring. Stirring was continued at 0C for 3h and at r.t. for 4 more hours. Water (70mL) was added and the solution was extracted with ethyl acetate (3×25mL). The combined organic layers were washed with brine (2×25mL) and dried (MgSO4). The solvent was evaporated to give a light brownish oil. Yield: 210mg (79%). 1H NMR (CDCl3): δ 1.44 (s, 9H, CH3), 2.51 (br m, 2H, H-3), 3.74 (s, 3H, OCH3), 4.38 (br m, 1H, NH), 5.03 (br m, 1 H, H-2), 5.07 (s, 1H, H-5cis), 5.10 (m, 1H, H-5trans), 5.65 (m, 1H, H-4), 13C NMR (CDCl3): δ 28.3 (q, CH3), 36.7 (t, C-3), 52.0 (d, C-2), 52.8 (q, OCH3), 79.7 (s, O-C), 118.9 (t, C-5), 132.3 (d, C-4), 155.1 (s, Boc), 172.4 (s, C-1).
With potassium carbonate; In acetone; for 4h;Reflux; 2-tert-Butoxycarbonylamino-pent-4-enoic acid (9.3 g, 43.3 mmol) in acetone (70 mL) is treated with solid potassium carbonate (11.9 g, 86.6 mmol) followed by methyl iodide (5.4 mL, 86.6 mmol). The resulting mixture is heated to reflux for 4 h and then allowed to cool to RT. The solvent is removed in vacuo and the crude residue is dissolved in EtOAc, washed with water, saturated sodium hydrogen carbonate solution, brine, dried (MgSO4) and concentrated in vacuo. The crude residue is purified by flash chromatography (SiCh, zso-hexane:EtOAc 7:3) to afford the title compound as a light-yellow oil.
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  • (1S,3S,4R)-2-(2-tert-Butoxycarbonylamino-pent-4-enoyl)-2-aza-bicyclo[2.2.1]hept-5-ene-3-carboxylic acid ethyl ester [ No CAS ]
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  • [ 107-11-9 ]
  • (1-allylcarbamoylbut-3-enyl)carbamic acid tert-butyl ester [ No CAS ]
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YieldReaction ConditionsOperation in experiment
With N-ethylmorpholine;; 1-hydroxy-7-aza-benzotriazole; HATU; In dichloromethane; at 20℃; for 12h; STEP B: Boc-Allyglycine-N-(2,4-dimethoxybenzyl)allylglycine methylester N-2,4-dimethoxybenzyl allylglycine methyl ester (as the free base) (7.79 g, 27.9 mmol) was dissolved in methylene chloride (90 mL), and then Boc-allyglycine-OH (6.0 g, 27.9 mmol), HOAt (3.8 g, 27.9 mmol), HATU (10.6 g, 27.9 mmol) and N-ethyl morpholine (3.6 mL, 27.9 mmol) were added to the reaction mixture. The reaction was allowed to proceed for 12 hours at room temperature after which time the solvent was removed and the crude mixture was dissolved/suspended in diethyl ether. The crude reaction was filtered through a pad of Celite to remove solid byproducts. The Celite was washed 3* with diethyl ether after which the combined ether solutions were poured into a separatory funnel and washed three times with 10% Na2CO3 in water, one time with saturated brine solution, three times with 1 N HCl and one time saturated brine. The organic layer was dried with anhydrous magnesium sulfate and the solvent was removed under reduced pressure. Final purification was accomplished by flash chromatography (3:1 hexanes/ethyl acetate) to yield a clear, colorless oil. 1H NMR (300 Hz, CDCl3, δ) 7.12, (d, 1H, 9 Hz); 6.45, (m, 2H); 5.7, (m, 1H), 5.35 (d, 1H, 9 Hz); 5.0, (m, 5H); 4.65, (d, 1H, 15 Hz); 4.35, (d, 1H, 15 Hz); 4.05, (m, 1H); 3.75, (m, 6H); 3.55, (s, 3H), 2.7, (m, 1H); 2.55 (m, 2H); 2.35 (m, 1H); 1.5 (s, 9H) HPLC Rt=3.95 MS m/z (% relative intensity, ion): 477 (30, M+H+), 499 (30, M+Na+) 151 (100, M+ of DMB)
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