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Chemical Structure| 494769-34-5

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Product Details of [ 494769-34-5 ]

CAS No. :494769-34-5
Formula : C9H12N2O3S
M.W : 228.27
SMILES Code : O=CC1=CSC(NC(OC(C)(C)C)=O)=N1
MDL No. :MFCD08275704
InChI Key :WJJQIZYBOFGKLA-UHFFFAOYSA-N
Pubchem ID :23138686

Safety of [ 494769-34-5 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319-H335
Precautionary Statements:P261-P305+P351+P338

Application In Synthesis of [ 494769-34-5 ]

* 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 [ 494769-34-5 ]

[ 494769-34-5 ] Synthesis Path-Downstream   1~21

  • 1
  • [ 494769-44-7 ]
  • [ 494769-34-5 ]
YieldReaction ConditionsOperation in experiment
78% With manganese(IV) oxide; In dichloromethane; for 2h;Heating / reflux; Step 3: (4-Formyl-thiazol-2-yl)-carbamic acid tert-butyl ester; (4-Hydroxymethyl-thiazol-2-yl)-carbamic acid tert-butyl ester (1.62 g, 6.95 mmol) was dissolved in 30 ml dichloromethane. Mangan(IV)oxid (3.65 g, 41.7 mmol) was added and the reaction mixture stirred at reflux for 2 hrs. The suspension was filtered through a dicalite speed plus pad and washed with dichloromethane. The solvents were evaporated and the desired compound was obtained as a light yellow solid (1.25 g, 78%), MS: m/e=229.2 (M+H+).
75% With Dess-Martin periodane; In dichloromethane; for 2h; (b) To a solution of 42a (10 g, 43.4 mmol) in 500 mL of DCM was added Dess Martin periodinane (30 g, 70.7 mmol) all at once. After 2 h, the reaction was concentrated by rotary evaporator, diluted with 1n NaOH, and extracted 3×EtOAc. The EtOAc extracts were dried over MgSO4. The solution was filtered and concentrated by rotary evaporator to give 7.4 g (75%) of the yellow solid 2-[(tert-butoxycarbonyl)amino]thiazole-4-carboxaldehyde 42b. 1H-NMR (400 MHz, CDCl3): delta 9.81 (s, 1H), 9.80 (bs, 1H), 7.73 (s, 1H), 1.47 (s, 9H).
75% With manganese(IV) oxide; In dichloromethane; at 20℃; (4-Formyl-thiazol-2-yl)-carbamic acid tert-butyl ester A solution of (4-hydroxymethyl-thiazol-2-yl)-carbamic acid tert-butyl ester (0.302 g, 1.31 mmol) in dry DCM (15 mL) is treated with manganese dioxide (1 .14 g, 13.1 mmol). The mixture is stirred at RT overnight. The reaction mixture is filtered over celite. The celite cake is washed with DCM (15 mL) and MeOH (15 ml_). The filtrate is evaporated under reduced pressure and dried under HV for 1 h to deliver the title compound (0.225 g, 75%) as a colorless solid; LC-MS A: tR = 0.71 min; [M+H]+ = 229.12.
75% With manganese(IV) oxide; In dichloromethane; at 20℃; (4-Formyl-thiazol-2-yl)-carbamic acid tert-butyl ester [0579] A solution of (4-hydroxymethyl-thiazol-2-yl)-carbamic acid tert-butyl ester (0.302 g, 1.31 mmol) in dry DCM (15 mL) is treated with manganese dioxide (1.14 g, 13.1 mmol). The mixture is stirred at RT overnight. The reaction mixture is filtered over celite. The celite cake is washed with DCM (15 mL) and MeOH (15 mL). The filtrate is evaporated under reduced pressure and dried under HV for 1 h to deliver the title compound (0.225 g, 75%) as a colorless solid; LC-MS A: tR=0.71 min; [M+H]+=229.12
75% With Dess-Martin periodane; In dichloromethane; at 20℃; for 16h; A solution of compound 2 (400 mg, 1.7 mmol) in DCM (10 mL) was added Dess-MaRTin (1.44 g, 3.4 mmol), then stirred at RT for 16 h. The resulting reaction mixture was quenched with water and extracted with DCM, dried and evaporated, purified by combiflash (methanol:DCM = 1:20) to give compound 3 (300 mg, 75%).
70% With Dess-Martin periodane; In dichloromethane; at 0 - 20℃; for 20h; A solution of Example 13 Part B compound (0.94 g; 4.08 mmol) in DCM (8 mL) was added dropwise to a 0 C. solution of Dess-Martin periodinane (1.82 g; 4.28 mmol) in DCM (8 mL). After 20 h at RT, the reaction was diluted with DCM (4 mL) and 1.0 N aqueous NaOH (6 mL). After stirring for 10 min, the mixture was filtered through Celite. The organic phase was washed with brine (10 mL), dried (MgSO4) and concentrated in vacuo. The residue was chromatographed (SiO2; continuous gradient from 0 to 50% EtOAc in hexanes over 12 min, hold at 50% EtOAc in hexanes for 8 min) to give Part A compound (0.65 g; 70%) as a white solid.
7 g With Dess-Martin periodane; In dichloromethane; at 20℃; for 2h; To a mixture of Compound AG (14 g, 60.79 mmol) in DCM (200 mL) was added Dess- Martin (30.9 g, 72.95 mmol) at rt. The mixture was kept for 2 hrs. Na2 S203 was added then the mixture was washed with water, aq. NaHC03. The organic layer was dried and concentrated to afford light yellow oil. The residue was purified by column chromatography in silica gel (PE: EA =10: 1) to give Compound AH (7.0 g) as light yellow oil.
7 g With Dess-Martin periodane; In dichloromethane; at 20℃; for 2h; To a mixture of Compound AG (14 g, 60.79 mmol) in DCM (200 mL) was added Dess-Martin (30.9 g, 72.95 mmol) at rt. The mixture was kept for 2 hrs. Na2O3 was added then the mixture was washed with water, aq. NaHCO3. The organic layer was dried and concentrated to afford light yellow oil. The residue was purified by column chromatography in silica gel (PE: EA=10:1) to give Compound AH (7.0 g) as light yellow oil.

  • 2
  • [ 494769-34-5 ]
  • [ 98020-38-3 ]
YieldReaction ConditionsOperation in experiment
83% With trifluoroacetic acid; In dichloromethane; at 0 - 20℃; for 20h; TFA (2.0 mL) was added to a 0 C. solution of Part A compound (0.64 g; 2.80 mmol) in DCM (4.0 mL). After 20 h at RT the reaction mixture was concentrated in vacuo. The residue was partitioned between EtOAc (10 mL) and sat. aqueous NaHCO3 (8 mL). The aqueous phase was isolated and extracted with EtOAc (5×8 mL). The combined organic extracts were dried (MgSO4) and concentrated in vacuo to give Part B compound (0.30 g; 83%) as a yellow solid.
  • 3
  • [ 494769-34-5 ]
  • [ 1001419-64-2 ]
YieldReaction ConditionsOperation in experiment
62% nBuLi (575 muL of a 1.6 M solution in hexanes; 0.920 mmol) was added dropwise to a cold (-78 C.) solution of Me(O)P(OEt)2 (134 muL; 0.920 mmol) in THF (0.30 mL). After 20 min a solution of Example 39 Part A compound (100 mg; 0.438 mmol) in THF (0.70 mL) was added dropwise. After 1 h at -78 C, the reaction was quenched by addition of AcOH (63 muL; 1.10 mmol). The reaction was warmed to RT and concentrated using a stream of Ar. The residue was partitioned between EtOAc (5 mL) and brine (4 mL). The organic phase was dried (MgSO4) and concentrated in vacuo. The crude product was chromatographed (SiO2; continuous gradient from 0 to 100% EtOAc in hexanes over 8 min, switch to 4% MeOH in EtOAc and hold for 6 min) to give Part A compound (104 mg; 62%) as a syrup.
  • 4
  • [ 494769-34-5 ]
  • [ 897934-64-4 ]
YieldReaction ConditionsOperation in experiment
50% (c) To a solution commercially available 3-iodopyridine (1.13 g, 5.5 mmol) in 15 mL of THF at 0 C was added a 2M solution of EtMgCl in THF (2.8 mL, 5.6 mmol) dropwise. After 1 h, added a solution of 42b (500 mg, 2.2 mmol) in 5 mL of THF. The reaction was allowed to warm to rt and stirred at for 1 hr. The reaction was quenched with water and extracted 2×EtOAC. The EtOAc extracts were dried over MgSO4, concentrated by rotary evaporator, and chromatographed on SiO2 using 50% hexanes in EtOAc then pure EtOAC to give 336 mg (50%) of 42c. MS found: (M+H)+=308.
  • 5
  • [ 494769-34-5 ]
  • C14H17N3O3S [ No CAS ]
YieldReaction ConditionsOperation in experiment
22% Example 43; (a) To a solution commercially available 4-iodopyridine (0.82 g, 4.0 mmol) in 10 mL of THF at 0 C was added a 2M solution of EtMgCl in THF (2.0 mL, 4.0 mmol) dropwise. After 1 h, added a solution of 42b (456 mg, 2.0 mmol) in 5 mL of THF. The reaction was allowed to warm to rt and stirred at for 1 hr. The reaction was quenched with water and extracted 2×EtOAC. The EtOAc extracts were dried over MgSO4, concentrated by rotary evaporator, and chromatographed on SiO2 using 50% hexanes in EtOAc then pure EtOAC to give 138 mg (22%) of 43a. MS found: (M+H)+=308.
YieldReaction ConditionsOperation in experiment
46.5% Step 2-1 Synthesis of 2-N-(1,1-dimethylethoxy-carbonyl)aminothiazole-4-carbaldehyde(22) (from alcohol 23) To a solution of 2.04 g (8.597 mmol) of alcohol 23 in CH2Cl2 (50 mL) were added 302 mg (0.86 mmol) of TPAP (tetrapropylammonium perruthenate), 3.11 g (26.547 mmol) of NMO (N-methylmorpholine N-oxide) and 16 g (2 g/1 mmol of alcohol) of 4 molecular sieve. After stirring for 2 hours at room temperature, the reaction mixture was filtered through a Celite pad and concentrated under reduced pressure. The residue was purified by flash column chromatography (silica, CH2Cl2:Hex:EtOAc=10:6:3) to give 950 mg (4.0 mmol) of aldehyde 22in 46.5% yield.
  • 7
  • [ 582-33-2 ]
  • [ 494769-34-5 ]
  • [ 79-46-9 ]
  • [ 494769-35-6 ]
YieldReaction ConditionsOperation in experiment
90.5% With acetic acid; In ethanol; dichloromethane; Step 3 Synthesis of N-isopropyl-alpha-[2-N-(1,1-dimethylethoxycarbonyl)aminothiazol-4-yl] nitrone (24) 2.22 9 (9.72 mmol) of compound 22, 3.47g (33.65 mmol) of 2-nitropropane (4), and 2.54 g (38.84 mmol) of zinc were placed in a round-bottomed flask along with 95% ethanol (50 mL) and cooled to 0 C. 4.67 g (77.77 mmol) of acetic acid was added slowly with stirring. The solution was allowed to come to room temperature, stirred for 6 hours. CH2Cl2 was added to the reaction mixture and it was filtered through a Celite pad and concentrated under reduced pressure. The residue was purified by short flash column chromatography (silica, Hex:EtOAc=1:1) to give 2.51 g (8.80 mmol) of compound 24 in 90.5% yield. 1H NMR (CDCl3): 8.71 (s, 1H), 7.63 (S, 1H), 4.21 (septet, J=6.6 Hz, 1H), 1.55 (s, 9H), 1.49 (d, J=6.6 Hz, 6H)
  • 8
  • [ 494769-34-5 ]
  • [ 594-70-7 ]
  • [ 494769-38-9 ]
YieldReaction ConditionsOperation in experiment
49% With acetic acid; In ethanol; dichloromethane; Step 1 Synthesis of N-tert-butyl-alpha-[2-N-(1,1-dimethylethoxycarbonyl) aminothiazol-4-yl]nitrone (28) 2.0 g (8.76 mmol) of compound 22, 5.42g (52.57 mmol) of 2-methyl-2-nitropropane (27), and 2.86 g (43.81 mmol) of zinc were placed in a round-bottomed flask along with 95% ethanol (50 mL) and cooled to 0 C. 4.21 g (70.11 mmol) of acetic acid was added slowly with stirring. The solution was allowed to come to room temperature, stirred for 6 hours. CH2Cl2 was added to the reaction mixture and it was filtered through a Celite pad and concentrated under reduced pressure. The residue was purified by short flash column chromatography (silica, Hex:EtOAc=1:1) to give 1.28 g (4.28 mmol) of compound 28 as a yellow solid in 49% yield. 1H NMR (CDCl3): 9.9 (br s, 1H), 8.82 (s, 1H), 7.87 (s, 1H), 1.60 (s, 9H), 1.54 (s, 6H); 13C NMR (CDCl3): 159.54, 152.35, 141.53, 125.78,
  • 9
  • CH2Cl2:EtOAc [ No CAS ]
  • [ 189512-01-4 ]
  • [ 494769-34-5 ]
YieldReaction ConditionsOperation in experiment
59.0% With hydrogenchloride; diisobutylaluminium hydride; In methanol; diethyl ether; dichloromethane; toluene; Step 2 Synthesis of 2-N-(1,1-dimethylethoxy-carbonyl)aminothiazole-4-carbaldehyde(22) (from ester 21) To a solution of 7.0 g (25.71 mmol) of ethyl ester 21 in CH2Cl2 (75 mL) were added 77 mL of diisobutylaluminum hydride (DIBAL-H, 1.0 M soln in toluene) for 20 minutes at -78 C. After stirring for 3 hours at that temperature, 30 mL of MeOH was added slowly to the reaction mixture, and then the reaction mixture was warmed to room temperature. Diethyl ether and 0.5 N HCl solution were added and the organic layer was separated. The solution was re-extracted with diethyl ether. The combined organic layers were washed with saturated NaHCO3 solution, dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by short flash column chromatography (silica, CH2Cl2:Hex:EtOAc=10:6:3 to CH2Cl2:EtOAc=1:1) to give 1.90 g (8.32 mmol) of solid aldehyde 22 in 32.4% yield and 3.5 g (15.20 mmol) of liquid alcohol 23 in 59.0% yield.
  • 10
  • [ 494769-34-5 ]
  • [ 930303-59-6 ]
YieldReaction ConditionsOperation in experiment
59% With diethylamino-sulfur trifluoride; In dichloromethane; at 20℃; for 16h; Step 4: (2-Difluoromethyl-thiazol-4-yl)-carbamic acid tert-butyl ester; To a solution of 1.25 g (5.5 mmol) <strong>[494769-34-5](4-formyl-thiazol-2-yl)-carbamic acid tert-butyl ester</strong> in 30 ml of dry methylene chloride were added 2.15 ml (16.4 mmol) diethylaminosulfur trifluoride (DAST). The mixture was stirred at room temperature for 16 hours. The reaction mixture was quenched with sat. NaHCO3- solution and extracted with water and methylene chloride. The combined organic extracts were dried with sodium sulfate, filtered and evaporated. The crude product was purified by flash chromatography on silica gel (heptane/ethyl acetate 4:1). The desired compound was obtained as a yellow solid (810 mg, 59%), MS: m/e=251.2 (M+H+).
  • 11
  • [ 494769-34-5 ]
  • [ 947179-19-3 ]
YieldReaction ConditionsOperation in experiment
60% Step 1: (4-Difluoromethylthiazol-2-yl)-carbamic acid tert-butyl ester To a solution of 1.25 g (5.5 mmol) <strong>[494769-34-5](4-formyl-thiazol-2-yl)-carbamic acid tert-butyl ester</strong> (CAS: [494769-34-5]) in 30 ml of dry methylene chloride were added 2.15 ml (16.4 mmol) diethylaminosulfur trifluoride (DAST). The mixture was stirred at room temperature for 16 hours. The reaction mixture was quenched with sat. NaHCO3- solution and extracted with water and methylene chloride. The combined organic extracts were dried with sodium sulfate, filtered and evaporated. The crude product was purified by flash chromatography on silica gel (heptane/ethyl acetate 4:1). The desired compound was obtained as a yellow solid (810 mg, 60%), MS: m/e=251.2 (M+H)+.
5.8 g With diethylamino-sulfur trifluoride; In ethanol; dichloromethane; at 20℃; To a solution of Compound AH (7.0 g, 31 mmol) in DCM (200 mL) and EtOH (100 mL) was added DAST (7.4 g, 46.05 mmol). The reaction mixture was stirred at room temperature overnight. The mixture was poured into water and diluted with DCM (200 mL), and then washed with water (100 mL), sat. NaHC03 (100 mL). The organic layer was dried and concentrated to afford light yellow oil. The residue was purified by column chromatography in silica gel (PE: EA =30: 1) to give the Compound AI (5.8 g) as a light yellow solid.
5.8 g With diethylamino-sulfur trifluoride; In ethanol; dichloromethane; at 20℃; To a solution of CompoundAR (7.0 g, 31 mmol) inDCM (200 mL) and EtOR (100 mL) was added DAST (7.4 g,46.05 mmol). The reaction mixture was stirred at room temSperature overnight. The mixture was poured into water anddiluted with DCM (200 mL), and then washed with water(100 mL), sat. NaHCO3 (100 mL). The organic layer wasdried and concentrated to afford light yellow oil. The residuewas purified by column chromatography in silica gel (PE:EA=30: 1) to give the Compound Al (5.8 g) as a light yellow
  • 12
  • [ 845305-83-1 ]
  • [ 494769-34-5 ]
  • [ 1138448-17-5 ]
YieldReaction ConditionsOperation in experiment
55% With sodium tris(acetoxy)borohydride; acetic acid; In dichloromethane; at 20℃; for 15h; To a stirred solution of compound IB (284 mg, 1.0 mmol), in 6 mL Of CH2Cl2 at room temperature was added N-boc-2-aminothiazole-4-carboxaldehyde (296 mg, 1.297 mmol). The mixture was then treated with sodium triacetoxyborohydride (275 mg, 1.298 mmol) and a catalytic amount of acetic acid. The reaction was allowed to stir for about 15 hours, then H2O was added and the aqueous mixture was extracted with CH2Cl2. The organic extract was washed with brine, dried over Na2SO4, and concentrated in vacuo to provide a crude yellow solid. The crude solid was purified using preparative TLC (CH2Cl2 - 7N NH3 in MeOH =30:1, v/v) to provide 271 mg of compound 24A (55%, MH+ = 497.22) as a light yellow solid.
  • 13
  • [ 850429-62-8 ]
  • [ 494769-34-5 ]
YieldReaction ConditionsOperation in experiment
With diisobutylaluminium hydride; In dichloromethane; at -78℃; for 2h; General procedure: To the solution of 4-sulfamoylbenzoic acid (200 mg, 0.53 mmol) inMeOH (8 mL) added SOCl2 (1348 muL, 1.84 mmol) at 0 C. The mixturewas stirred at 40 C for 2 h, and then concentrated. Ester (214 mg,1.00 mmol) and (Boc)2O (238 mg, 1.09 mmol) were dissolved in DCM(8 mL). Et3N (138 muL, 1 mmol) and DMAP (12.2 mg, 0.1 mmol) wereadded and the mixture was stirred at rt. for 1.5 h. The solution wasconcentrated and purified to afford methyl 4-(N-(tert-butoxycarbonyl)sulfamoyl)benzoate. DIBAL-H (2 mL, 2 mmol) was added slowly tomethyl benzoate (300 mg, 1.00 mmol) in DCM (8 mL) at -78 C and themixture was stirred at -78 C for 2 h. The reaction was quenched by MeOH (2 mL), and then warmed to 0 C and added 10% citric acidunder stirring. The mixture was extracted with DCM, and the organicswere washed, dried, concentrated and purified to afford 4-formylbenzenesulfonamide.Using 4-formylbenzenesulfonamide, thecompound 44 was obtained from 5 by the general procedure as above.To the solution of 44 (95 mg, 0.20 mmol) in DCM (4 mL) added TFA(300 muL, 0.04 mmol). The mixture was stirred at rt. for 1 h. The solutionwas adjusted to pH 7-8 by NaHCO3. The mixture was extracted withEA, and the organics were washed, dried, concentrated and purified toafford 17, 54% yield for five steps, 94.0% HPLC purity.
  • 14
  • [ 1108653-08-2 ]
  • [ 494769-34-5 ]
YieldReaction ConditionsOperation in experiment
With sodium chlorite; In water; at 20℃; for 16h;Inert atmosphere; A mixture of tert-butyl (4-((methoxy(methyl)amino)methyl)thiazol-2-yl)carbamate (125mg) in THF (6 mL) and NaCIO (0.86 mL) in water (0.6 mL) was stirred at rt for 16h. The solvent was evaporated in vacuo. The mixture was diluted with DCM and sat. aq NaHC03, the layers were separated and the aq. phase was extracted with DCM. The combined org. layers were washed filtrated off over phase separator and evaporated in vacuo. The crude (135mg, yellow oil) was used in the next step without purification. LC-MS (A): tR = 0.78 min; [M+H]+: not visible.
  • 15
  • [ 1100350-49-9 ]
  • [ 494769-34-5 ]
  • 16
  • [ 24424-99-5 ]
  • [ 494769-34-5 ]
  • 17
  • [ 494769-34-5 ]
  • (1S)-1-cyclopropylethan-1-amine [ No CAS ]
  • (S)-tert-butyl 4-((1-cyclopropylethylamino)methyl)thiazol-2-ylcarbamate [ No CAS ]
YieldReaction ConditionsOperation in experiment
100% With sodium tetrahydroborate; In methanol; at 20℃; for 16h; To a stirring solution of compound 3 (0.1 g, 0.44 mmol) and (5)-i -cyclopropylethanamine (56 mg, 0.66 mmol) in MeOH (10 mL) was added NaBH4 (35 mg, 0.88 mmol). The resulting reaction mixture was stirred at RT for 16 h. The reaction mixture was concentrated, EtOAc was added and washed with water and brine, dried and evaporated, purified by combiflash (methanol:DCM = 1:20) to give compound 4 (130 mg, 100%). LC-MS: m/z = 198.2 [M+H-Boc]
  • 18
  • [ 189512-01-4 ]
  • [ 494769-34-5 ]
  • 19
  • [ 494769-34-5 ]
  • tert-butyl 4-((N-((S)-1-cyclopropylethyl)-2-((S)-2,5-dioxo-2',3'-dihydrospiro[imidazolidine-4,1'-indene]-1-yl)acetamido)methyl)thiazol-2-ylcarbamate [ No CAS ]
  • 20
  • [ 50533-97-6 ]
  • [ 494769-34-5 ]
  • tert-butyl (4-[4-(dimethylamino)piperidin-1-yl]methyl}-1,3-thiazol-2-yl)carbamate [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% tert-butyl (4-formyl-1 ,3-thiazol-2-yl)carbamate (200 mg, 0.88 mmol) in DMA (3 mL) was treated with N,N- dimethylpiperidin-4-amine (0.155 mL, 1.3 mmol) and stirred at rt over 1 h. AcOH (0.025 mL, 0.43 mmol) and sodium triacetoxyborohydride (465 mg, 2.19 mmol) were added to the reaction and stirred at rt for 20 h. The residue was partitioned between EtOAc and saturated aqueous NaHC03. The organic layer was dried over Na2S04 and evaporated to dryness. The crude was purified by column chromatography over silica gel (DCM:7N NH3 in MeOH = 9:1) to give the title compound as colourless oil (225 mg, 75%).1H NMR (500 MHz, DMSO-de) delta ppm 1.27 - 1.38 (m, 2 H) 1.47 (s, 9 H) 1.61 - 1.75 (m, 2 H) 1.87 - 2.03 (m, 3 H) 2.13 (s, 6 H) 2.78 - 2.89 (m, 2 H) 3.37 (s, 2 H) 6.85 (s, 1 H).HRMS (ESI+): calcd. for C16H29N4O2S [M + H]+341.2006; found 341.2008.
  • 21
  • [ 494769-34-5 ]
  • [ 885518-50-3 ]
  • C16H18BrN5O2S [ No CAS ]
YieldReaction ConditionsOperation in experiment
With diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate; trifluoroacetic acid; In methanol; dichloromethane; at 45℃; for 4h; General procedure: To the solution of 4-sulfamoylbenzoic acid (200 mg, 0.53 mmol) inMeOH (8 mL) added SOCl2 (1348 muL, 1.84 mmol) at 0 C. The mixturewas stirred at 40 C for 2 h, and then concentrated. Ester (214 mg,1.00 mmol) and (Boc)2O (238 mg, 1.09 mmol) were dissolved in DCM(8 mL). Et3N (138 muL, 1 mmol) and DMAP (12.2 mg, 0.1 mmol) wereadded and the mixture was stirred at rt. for 1.5 h. The solution wasconcentrated and purified to afford methyl 4-(N-(tert-butoxycarbonyl)sulfamoyl)benzoate. DIBAL-H (2 mL, 2 mmol) was added slowly tomethyl benzoate (300 mg, 1.00 mmol) in DCM (8 mL) at -78 C and themixture was stirred at -78 C for 2 h. The reaction was quenched by MeOH (2 mL), and then warmed to 0 C and added 10% citric acidunder stirring. The mixture was extracted with DCM, and the organicswere washed, dried, concentrated and purified to afford 4-formylbenzenesulfonamide.Using 4-formylbenzenesulfonamide, thecompound 44 was obtained from 5 by the general procedure as above.To the solution of 44 (95 mg, 0.20 mmol) in DCM (4 mL) added TFA(300 muL, 0.04 mmol). The mixture was stirred at rt. for 1 h. The solutionwas adjusted to pH 7-8 by NaHCO3. The mixture was extracted withEA, and the organics were washed, dried, concentrated and purified toafford 17, 54% yield for five steps, 94.0% HPLC purity.
 

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