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CAS No. : | 279255-90-2 | MDL No. : | MFCD09834884 |
Formula : | C14H17NO3 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | XIMLBZMOOXHPJQ-UHFFFAOYSA-N |
M.W : | 247.29 | Pubchem ID : | 21865484 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
11%; 55%; 12% | With sodium tris(acetoxy)borohydride; In 1,2-dichloro-ethane; at 20℃; for 8h; | D-Leucinamide (1.0 g, 6.0 mmol), 1-(t-butyloxycarbonyl)-5-formylindole (Example 1, 1.23 g, 5.0 mmol) and DCE (15 mL) were mixed at room temperature. Sodium triacetoxyborohydride (1.48 g, 7.0 mmol) was added in one portion with vigorous stirring. After 2 h, another portion (0.15 g, 0.7 mmol) was added and stirring was continued for an additional 6 h. The reaction mixture was diluted with a saturated NaHCO3 solution (10 mL). Three extractions with EtOAc, washing the combined organic layers with brine, drying over Na2SO4 and filtration provided a solution. Removal of solvent in vacuo afforded an oil. Column chromatography (DCM:MeOH:95:5) provided three fractions, after removal of solvent in vacuo: (1) 1-(t-Butyloxycarbonyl)-5-hydroxymethylindole (162 mg, 11% yield, Rf=0.5): 1H NMR (CDCl3, 300 MHz): 8.11 (d, 1H, J=8), 7.61 (d, 1H, J=2), 7.54 (s, 1H), 7.31 (dd, 1H, J=8,2), 6.55 (d, 1H, J=3), 4.75 (s, 2H), 1.69 (s, 9H); (2) 2R-bis-(1-t-butyloxycarbonylindol-5-ylmethyl)amino-4-methylpentanamide BMS594447 (382 mg, 12% yield, Rf=0.4): 1H NMR (CDCl3, 300 MHz): 8.1 (d, 2H, J=8), 7.61 (d, 2H, J=2), 7.52 (s, 2H), 7.31 (dd, 2H, J=8,2), 6.62 (m, 1H), 6.56 (d, 2H, J=4), 6.05 (br s, 1H), 3.85 (d, 2H, J=16), 3.66 (d, 2H, J=16), 3.35 (m, 1H), 1.69 (s, 18H), 0.96 (d, 3H, J=7), 0.87 (d, 3H, J=7); MS (ES+): 589.4 (C35H45N3O5) and (3) the title product (986 mg, 55% yield, Rf=0.3): 1H NMR (CDCl3, 300 MHz): 8.10 (d, 1H, J=8), 7.61 (d, 1H, J=2), 7.49 (d, 1H, J=1), 7.28-7.20 (m, 3H), 6.55 (d, 1H, J=4), 3.93 (d, 1H, J=16), 3.77 (d, 1H, J=16), 3.28-3.20 (m, 1H), 1.69 (s, 9H), 0.94 (d, 3H, J=7), 0.85 (d, 3H, J=7); MS (ES+): 360 (C20H30N3O3, M++H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With diisobutylaluminium hydride; In tetrahydrofuran; methanol; water; toluene; | Step 2 To a solution of N-tert-butoxycarbonylindole-5-carboxylic acid methyl ester (23.6 g, 85.7 mmol) in dry tetrahydrofuran (225 mL) at -78 C. was added 1.5 M DIBALH in toluene (171 mL, 257 mmol). After 2 h, the reaction mixture was quenched by the slow addition of methanol (45 mL), water (60 mL), and saturated aqueous NH4Cl (30 mL). The cold bath was removed and after stirring for an additional 1 h, the reaction mixture was filtered over Celite. The Celite cake was washed with tetrahydrofuran and the filtrate was concentrated to remove the more volatile tetrahydrofuran. The biphasic mixture was extracted with ethyl acetate. The combined organic layers were washed with water and the aqueous layer back extracted with ethyl acetate. The combined organic layers were washed with brine, dried over magnesium sulfate, and concentrated to afford N-tert-butoxycarbonylindol-5-yl methanol (21.2 g). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tributylphosphine; In benzene; | Step 4 To an ice-cooled mixture of 2(R)-(4-methoxybenzenesulfonylamino)-3-methylbutyric acid benzyl ester (5 g, 13.25 mmol) [prepared as described in Example 2 above], N-tert-butoxycarbonyl-5-indole methanol (3.8 g, 14.6 mmol) and tributylphosphine (3.6 mL, 14.6 mmol) in dry benzene (60 mL) was added [1,1'-azodicarbonyl]dipiperidine (3.68 g, 14.6 mmol). The reaction mixture was stirred overnight at room temperature and then chromatographed on a silica gel column eluding with (5-10%) ethyl acetate/hexanes to give of 2(R)-[(N-tert-butoxy-carbonylindol-5-ylmethyl)-(4-methoxybenzenesulfonyl)amino]-3-methylbutyric acid benzyl ester (6.5 g) as a white foamy semi-solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With ammonium chloride; diisobutylaluminium hydride; In tetrahydrofuran; methanol; water; ethyl acetate; toluene; | Step 3 To a cooled solution (-78 C.) of methyl (N-tert-butoxycarbonyl)indole-5-carboxylate (7.6 g, 27.9 mmol) in dry tetrahydrofuran (75 mL) was added diisobutylaluminum hydride (57 mL, 1.5 M in toluene) via syringe over 5 min. After 1.5 h, the reaction mixture was quenched by careful addition of methanol (15 mL) and allowed to warm to room temperature over 45 min. Water (20 mL) and a saturated solution of ammonium chloride(10 mL) was added with vigorous stirring and the resultant inorganic precipitate was removed by filtration. The filtrate was condensed on the roto-evaporator and the residue was partitioned between a 1:1 mixture of ethyl acetate/water (160 mL). The ethyl acetate phase was washed with brine and the aqueous phases back extracted with ethyl acetate. The organic phase was combined, dried with magnesium sulfate, filtered and concentrated to provide (N-tert-butoxycarbonyl)indole-5-methanol (7.35 g) as a semi-viscous yellow oil which was used in the next step without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In dichloromethane; | Step 3 To a solution of <strong>[279255-90-2]N-tert-butoxycarbonylindol-5-yl methanol</strong> (2.56 g, 10.35 mmol) in dry methylene chloride (60 mL) was added manganese oxide (9 g, 103.5 mmol). The reaction mixture was stirred for 3 h at room temperature and then heated at reflux. After 3 h, the heterogeneous slurry was filtered through Celite and concentrated to afford N-tert-butoxycarbonyl-5-formylindole (2.5 g). | |
With manganese(IV) oxide; In dichloromethane; at 40℃; for 25h; | A solution of tert-butyl 5-([tert-butyl(dimethyl)silyl]oxy}methyl)-1H-indole-1- carboxylate (1-6, 13.0 g, 36.0 mmol, 1 equiv) and triethylamine trihydrofluoride (5.86 mL, 36.0 ralphamol, 1.00 equiv) in acetonitrile (150 mL) was stirred at 23 C for 20 h. The reaction mixture was concentrated, and the residue was partitioned between saturated aqueous sodium bicarbonate solution and ethyl acetate (2 x 200 mL). The combined organic layers were washed with brine, dried over sodium sulfate and concentrated. The residue was purified by flash column chromatography (hexanes initially, grading to 60% EtOAc in hexanes) to provide the intermediate alcohol. A mixture of the alcohol and manganese (IV) oxide (6.25 g, 71.9 mmol, 2.00 equiv) in dichloromethane (200 mL) was heated at 40 C for 20 h. Additional manganese(IV) oxide (3.13 g, 36.0 mmol, 1.00 equiv) was added and heating was continued for 5 h. The solids were filtered and washed with dichloromethane (3 x 100 mL). The combined filtrate EPO <DP n="69"/>was concentrated to give tert-butyl 5-formyl-1H-indole-1-carboxylate (5-1) as a colorless oil. 1H NMR (300 MHz, CDCl3) delta 10.07 (s, 1H), 8.29 (d, 1H, J = 8.8 Hz), 8.10 (d, 1H, J = 1.6 Hz), 7.86 (dd, 1H, J = 8.8, 1.8 Hz), 7.69 (d, 1H, J = 4.0 Hz), 6.70 (dd, 1H, J = 3.7, 0.6 Hz), 1.70 (s, 9H). LRMS m/z (M+H- CH3) 231.2 found, 231.1 required. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine tris(hydrogen fluoride); In acetonitrile; at 23℃; for 20h; | A solution of tert-butyl 5-([tert-butyl(dimethyl)silyl]oxy}methyl)-1H-indole-1- carboxylate (1-6, 13.0 g, 36.0 mmol, 1 equiv) and triethylamine trihydrofluoride (5.86 mL, 36.0 ralphamol, 1.00 equiv) in acetonitrile (150 mL) was stirred at 23 C for 20 h. The reaction mixture was concentrated, and the residue was partitioned between saturated aqueous sodium bicarbonate solution and ethyl acetate (2 x 200 mL). The combined organic layers were washed with brine, dried over sodium sulfate and concentrated. The residue was purified by flash column chromatography (hexanes initially, grading to 60% EtOAc in hexanes) to provide the intermediate alcohol. A mixture of the alcohol and manganese (IV) oxide (6.25 g, 71.9 mmol, 2.00 equiv) in dichloromethane (200 mL) was heated at 40 C for 20 h. Additional manganese(IV) oxide (3.13 g, 36.0 mmol, 1.00 equiv) was added and heating was continued for 5 h. The solids were filtered and washed with dichloromethane (3 x 100 mL). The combined filtrate EPO <DP n="69"/>was concentrated to give tert-butyl 5-formyl-1H-indole-1-carboxylate (5-1) as a colorless oil. 1H NMR (300 MHz, CDCl3) delta 10.07 (s, 1H), 8.29 (d, 1H, J = 8.8 Hz), 8.10 (d, 1H, J = 1.6 Hz), 7.86 (dd, 1H, J = 8.8, 1.8 Hz), 7.69 (d, 1H, J = 4.0 Hz), 6.70 (dd, 1H, J = 3.7, 0.6 Hz), 1.70 (s, 9H). LRMS m/z (M+H- CH3) 231.2 found, 231.1 required. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With phosphorus tribromide; In diethyl ether; dichloromethane; for 0.666667h; | To an ice-cold solution OF 5-HYDROXYMETHYLINDOLE-1-CARBAMIC acid tert-butyl ester (0.51 g, 2.1 mmol) in 4: 1 ET2O/CH2CL2 (4 ML) was added PBr3 (0.2 mL, 2.2 mmol), and the reaction mixture was stirred for 40 min. The reaction mixture was diluted with CH2C12, washed a saturated solution OF NAHC03 (3 x 10 mL), dried (NA2SO4), filtered, and the solvent was removed under reduced pressure to provide 5-BROMOMETHYL-INDOLE-1- carbamic acid tert-butyl ester as a yellow solid (0.59 g, 93%). IH NMR (300 MHz, CDC13) 8 8.07 (d, J= 9 Hz, 1H), 7.68-7. 62 (m, 2H), 7.33 (d, 7= 9 Hz, 1H), 6.60 (s, 1H), 4.68 (s, 2H), 1.67 (s, 9H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With diisobutylaluminium hydride; In tetrahydrofuran; at -78℃; for 2.5h; | To a-78C solution of 5-(carboxymethyl)i-indole-1-carbamic acid tert-butyl ester (10. 8 g, 39 mmol) in THF (180 ML) was added DIBAL (127 ML of a 1 M solution in THF, 127 mmol), and the reaction mixture was stirred for 2.5 h. The reaction was quenched with 1: 1 1 N HCI/MeOH (100 mL), the reaction mixture was warmed to room temperature, diluted with CH2Cl2 (100 mL), and separated. The organic solution was washed with saturated Rochelle salt, dried (NA2S04), filtered, and concentrated under reduced pressure. Purification by flash column chromatography (silica, 1: 1 EtOAc/hexanes) provided 5-hydroxymethylindole-1-carbamic acid tert-butyl ester as a yellow oil (6.5 g, 68%) :H NMR (300 MHz, CDC) 8 8.07 (d, J = 9 Hz, 1H), 7.59 (d, J = 6 Hz, 1H), 7.54 (s, 1H), 7.28 (d, J = 9 Hz, 1H), 6.58 (D, J = 6 Hz, 1H), 4.73 (s, 2H), 1.97 (s, 9H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With methanol; sodium tetrahydroborate; at 0 - 20℃; for 3h; | To a solution of tert-butyl 5-formyl-1H-indo . g, 12.23 mmol) in methanol (30 mL) was added sodium tetrahydroborate (0.463 g, 12.23 mmol) at 0 C. The reaction mixture was stirred at 0 C for 3 hours then overnight at room temperature. The resulting solution was diluted with water (40 mL), then extracted with ethyl acetate (3 x 30 mL). The organic layers were combined, washed with aqueous sodium carbonate and brine, dried and concentrated under vacuum to afford tert-butyl 5-(hydroxymethyl)-1H-indole-1- carboxylate (2.5 g, 10.11 mmol, 83% yield) as a yellow oil. LCMS m/z = 270.3 [M+Na]+. |
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