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CAS No. : | 174148-03-9 | MDL No. : | MFCD00673782 |
Formula : | C25H28N2O6 | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | UPXRTVAIJMUAQR-BTYIYWSLSA-N |
M.W : | 452.50 | Pubchem ID : | 2756134 |
Synonyms : |
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Chemical Name : | (4S)-4-N-Fmoc-amino-1-Boc-L-proline |
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 |
---|---|---|
93% | With N-ethyl-N,N-diisopropylamine; HATU; In N,N-dimethyl-formamide; at 20℃; for 3h; | To a solution of (2S,4S)-4-(((9H-fluoren-9-yl)methoxy)carbonylamino)-1-(tert-butoxycarbonyl)pyrrolidine-2-carboxylic acid (10 g, 22.2 mmol), (R)-1,2,3,4-tetrahydronaphthalen-1-amine (3.26 g, 22.2 mmol) and DIEA (14.28 g, 111 mmol) in DMF (100 mL) was added HATU (9.26 g, 24.4 mmol). The solution was stirred at room temperature for 3 h. The reaction was quenched by the addition of 200 mL H2O and then extracted with ethyl acetate (200 mL x 3). The combined organic layer was washed with brine, dried over anhydrous Na2SO4 and concentrated under vacuum. The crude residue was purified by flash column chromatography with 10~50% ethyl acetate in petroleum ether to afford (2S,4S)-tert-butyl 4-(((9H-fluoren-9-yl)methoxy)carbonylamino)-2-((R)-1,2,3,4-tetrahydronaphthalen-1-ylcarbamoyl)pyrrolidine-1-carboxylate (12.0 g, 93%) as a white solid. MS (ESI) calculated for (C35H39N3O5) [M+H]+, 582.3; found, 582.0. |
87% | To a solution of (2S,45)-Boc-gamma-(Fmoc-amino)-proline (Chem-Impex, 6.00 g, 13.3 mmol) in DMF (20 mL) at 0 C were added EDC (3.05 g, 15.9 mmol), HOAt (2.17 g, 15.9 mmol) and NMM (4.38 mL, 39.8 mmol). The reaction mixture was stirred at ice bath temperature for 20 min then treated with a solution of (R)- 1,2,3, 4- tetrahydronaphthalen- 1 -amine (Alfa Aesar, 2.15 g, 14.6 mmol) in DMF (2 mL). The reaction mixture was stirred at rt for 1 h and cold water (100 mL) was added to the reaction mixture. The solid that formed was collected by filtration and washed with cold water (100 mL). The solid was dissolved in (( (200 mL) and the organic solution was washed with 5% aq. citric acid solution and brine, dried over MgS04, and filtered. The filtrate was concentrated in vacuo. The residue was dissolved in CH2CI2 and purified by flash column chromatography (gradient elution from 10 to 30% EtOAc in CH2CI2) provided the title compound (6.70 g, 87%) as a light tan solid. *H NMR (400 MHz, CDCI3) δ 7.79 (d, J= 7.5 Hz, 2H), 7.67 (d, J= 7.3 Hz, 2H), 7.42 (td, J= 7.2, 4.0 Hz, 2H), 7.37 - 7.03 (m, 6H), 5.22 (br. s., 1H), 4.57 - 4.23 (m, 5H), 3.68 - 3.49 (m, 2H), 2.91 - 2.74 (m, 2H), 2.52 (d, J= 13.4 Hz, 1H), 2.35 - 2.21 (m, 1H), 2.14 (d, J= 5.1 Hz, 1H), 1.97 - 1.80 (m, 3H), 1.44 (s, 9H); MS(ESI+) m/z 582.2 (M+H)+ | |
87% | To a solution of (2S,4S)-Boc-4-(Fmoc-amino)-proline (Chem-Impex, 6.00 g, 13.3 mmol) in DMF (20 mL) at 0 C were added EDC (3.05 g, 15.9 mmol), HOAt (2.17 g, 15.9 mmol) and NMM (4.38 mL, 39.8 mmol). The reaction mixture was stirred at ice bath temperature for 20 min then treated with a solution of (R)- 1 ,2, 3,4- tetrahydronaphthalen-1 -amine (Alfa Aesar, 2.15 g, 14.6 mmol) in DMF (2 mL). The reaction mixture was stirred at rt for 1 h and cold water (100 mL) was added to the reaction mixture. The solid that formed was collected by filtration and washed with cold water (100 mL). The solid was dissolved in CH2CI2 (200 mL) and the organic solution was washed with 5% aq. citric acid solution and brine, dried over MgS04, and filtered. The filtrate was concentrated in vacuo. The residue was dissolved in CH2C12 and purified by flash column chromatography (gradient elution from 10 to 30% EtOAc in CH2C12)provided the title compound (6.70 g, 87%) as a light tan solid. 1H NMR (400 MHz, CDCls) δ 7.79 (d, J= 7.5 Hz, 2H), 7.67 (d, J= 7.3 Hz, 2H), 7.42 (td, J= 7.2, 4.0 Hz, 2H), 7.37 - 7.03 (m, 6H), 5.22 (br. s., 1H), 4.57 - 4.23 (m, 5H), 3.68 - 3.49 (m, 2H), 2.91 - 2.74 (m, 2H), 2.52 (d, J= 13.4 Hz, 1H), 2.35 - 2.21 (m, 1H), 2.14 (d, J= 5.1 Hz, 1H), 1.97 - 1.80 (m, 3H), 1.44 (s, 9H); MS(ESI+) m/z 582.2 (M+ |
87% | A) (2S,4S)-tert-Butyl 4-((((9H-fluoren-9-yl)methoxy)carbonyl)amino)-2-(((R)- 1 ,2,3 ,4-tetrahydronaphthalen- 1 -yl)carbamoyl)pyrrolidine- 1 -carboxylate [00147] To a solution of (2S,4S)-Boc-gamma-(Fmoc-amino)-proline (Chem-Impex, 6.00 g, 13.3 mmol) in DMF (20 mL) at 0 C were added EDC (3.05 g, 15.9 mmol), HOAt (2.17 g, 15.9 mmol) and 4-methylmorpholine (4.38 mL, 39.8 mmol). The reaction mixture was stirred at ice bath temperature for 20 min then treated with a solution of (R)- 1,2,3,4-tetrahydronaphthalen-l -amine (ALFA AESAR, 2.15 g, 14.6 mmol) in DMF (2 mL). The reaction mixture was stirred at rt for 1 h and cold water (100 mL) was added to the reaction mixture. The solid that formed was collected by filtration and washed with cold water (100 mL). The solid was dissolved in CH2CI2 (200 mL) and the organic solution was washed with 5% aq. citric acid solution and brine, dried over MgS04, and filtered. The filtrate was concentrated in vacuo. The residue was dissolved in CH2CI2 and purified by flash column chromatography (gradient elution from 10 to 30% EtOAc in CH2CI2) provided the title compound (6.7 g, 87%) as a light tan solid. XH NMR (400 MHz, CDCI3) δ 7.79 (d, J= 7.5 Hz, 2H), 7.67 (d, J= 7.3 Hz, 2H), 7.42 (td, J= 7.2, 4.0 Hz, 2H), 7.37 - 7.03 (m, 6H), 5.22 (br. s., 1H), 4.57 - 4.23 (m, 5H), 3.68 - 3.49 (m, 2H), 2.91 - 2.74 (m, 2H), 2.52 (d, J= 13.4 Hz, 1H), 2.35 - 2.21 (m, 1H), 2.14 (d, J= 5.1 Hz, 1H), 1.97 - 1.80 (m, 3H), 1.44 (s, 9H); MS(ESI+) m/z 582.2 (M+H)+. | |
87% | To a solution of (2S,4S)-Boc-4-(Fmoc-amino)-proline (Chem-Impex, 6.00 g, 13.3 mmol) in DMF (20 mL) at 0 C. were added EDC (3.05 g, 15.9 mmol), HOAt (2.17 g, 15.9 mmol) and NMM (4.38 mL, 39.8 mmol). The reaction mixture was stirred at ice bath temperature for 20 min then treated with a solution of (R)-1,2,3,4-tetrahydronaphthalen-1-amine (ALFA AESAR, 2.15 g, 14.6 mmol) in DMF (2 mL). The reaction mixture was stirred at rt for 1 h and cold water (100 mL) was added to the reaction mixture. The solid that formed was collected by filtration and washed with cold water (100 mL). The solid was dissolved in CH2Cl2 (200 mL) and the organic solution was washed with 5% aq. citric acid solution and brine, dried over MgSO4, and filtered. The filtrate was concentrated in vacuo. The residue was dissolved in CH2Cl2 and purified by flash column chromatography (gradient elution from 10 to 30% EtOAc in CH2Cl2) provided the title compound (6.70 g, 87%) as a light tan solid. 1H NMR (400 MHz, CDCl3) δ 7.79 (d, J=7.5 Hz, 2H), 7.67 (d, J=7.3 Hz, 2H), 7.42 (td, J=7.2, 4.0 Hz, 2H), 7.37-7.03 (m, 6H), 5.22 (br. s., 1H), 4.57-4.23 (m, 5H), 3.68-3.49 (m, 2H), 2.91-2.74 (m, 2H), 2.52 (d, J=13.4 Hz, 1H), 2.35-2.21 (m, 1H), 2.14 (d, J=5.1 Hz, 1H), 1.97-1.80 (m, 3H), 1.44 (s, 9H); MS(ESI+) m/z 582.2 (M+H)+. | |
87% | To a solution of (2S,4S)-l3oc-gamma-(Fmoc- amino)-proline (Chem-Impex, 6.00 g, 13.3 mmol) in DMF (20 mE) at 00 C. were added EDC (3.05 g, 15.9 mmol), HOAt (2.17 g, 15.9 mmol) and NMM (4.38 mE, 39.8 mmol). The reaction mixture was stirred at ice bath temperature for 20 mm then treated with a solution of (R)-1 ,2, 3,4-tetrahydronaphthalen- i-amine (Alfa Aesar, 2.15 g, 14.6 mmol) in DMF (2 mE). The reaction mixture was stirred at it for 1 hand cold water (100 mE) was added to the reaction mixture. The solid that formed was collected by filtration and washed with cold water (100 mE). The solid was dissolved in CH2C12 (200 mE) and the organic solution was washed with 5% aq. citric acid solution and brine, dried over MgSO4, and filtered. The filtrate was concentrated in vacuo. The residue was dissolved in CH2C12 and purified by flash colunm chromatography (gradient elution from 10 to 30% EtOAc in CH2C12) provided the title compound (6.70 g, 87%) as a light tan solid. ‘H NMR (400 MHz, CDC13) ? 7.79 (d, J=7.5 Hz, 2H), 7.67 (d, J7.3 Hz, 2H), 7.42 (td, J=7.2, 4.0 Hz, 2H), 7.37-7.03 (m, 6H), 5.22 (bt s., 1H), 4.57-4.23 (m, 5H), 3.68-3.49 (m, 2H), 2.91-2.74 (m, 2H), 2.52 (d, J=13.4 Hz, 1H), 2.35-2.21 (m, 1H), 2.14 (d, J=5.i Hz, 1H), 1.97- 1.80 (m, 3H), 1.44 (s, 9H); MS(ESI) mlz 582.2 (M+H). | |
9.6 g | With N-ethyl-N,N-diisopropylamine; HATU; In N,N-dimethyl-formamide; at 0℃; for 4h; | To a solution of (2S,4S )-4-(9H-fluoren-9 -ylmethoxycarbonylamino)-pyrrolidine- 1,2-dicarboxylic acid 1-tert-butyl ester (Aldrich) (7.5 g, 16.593 mmol) in DMF (100 mL) were addedHATU (6.93 g, 18.252 mmol) and DIPEA (14.36 mL, 82.965 mmol) and the mixture was cooled to 0 C. (R)-(1,2,3,4-tetrahydro-naphthalen-1-yl)amine (2.44 g, 16.593 mmol) was added dropwise and the cooling bath removed. After 4 h the mixture was diluted with ethyl acetate, washed with water, dried over sodium sulfate and concentrated to afford the title compound as an off white solid (9.6 g) which was used without purification. LC-MS: 582 (M+H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | 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 N,N-dimethyl-formamide; at 20℃; for 3h; | To a solution of (2S,4S)-4-(((9H-fluoren-9-yl)methoxy)carbonylamino)-l-(tert- butoxycarbonyl)pyrrolidine-2-carboxylic acid (10 g, 22.2 mmol), (R)-l,2,3,4- tetrahydronaphthalen-l -amine (3.26 g, 22.2 mmol) and DIEA (14.28 g, 111 mmol) in DMF (100 mL) was added HATU (9.26 g, 24.4 mmol). The solution was stirred at room temperature for 3 h. The reaction was quenched by the addition of 200 mL H20 and then extracted with ethyl acetate (200 mL x 3). The combined organic layer was washed with brine, dried over anhydrous Na2S04 and concentrated under vacuum. The crude residue was purified by flash column chromatography with 10-50% ethyl acetate in petroleum ether to afford (2S,4S)-tert-butyl 4-(((9H-fluoren-9-yl)methoxy)carbonylamino)-2-((R)-l,2,3,4- tetrahydronaphthalen-l-ylcarbamoyl)pyrrolidine-l-carboxylate (12.0 g, 93%) as a white solid. MS (ESI) calculated for (C35H39N3O5) [M+H]+, 582.3; found, 582.0. |