Dimethyl Sulfate → HCID 67264350, compound

HRID 1040632Notes

Reaction equation

HRID 1040632 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH:17]2[CH2:18][CH2:19][CH:9]1[C:10]1[C:11]([OH:28])=[C:12]([NH:20][C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])[CH:13]=[CH:14][C:15]=1[CH2:16]2)=[O:7])([CH3:4])([CH3:3])[CH3:2].S(OC)(O[CH3:33])(=O)=O.C(=O)([O-])[O-].[Cs+].[Cs+].O1CCOCC1>O>[C:1]([O:5][C:6]([N:8]1[CH:17]2[CH2:18][CH2:19][CH:9]1[C:10]1[C:11]([O:28][CH3:33])=[C:12]([NH:20][C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])[CH:13]=[CH:14][C:15]=1[CH2:16]2)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 4

HCID 6497Dimethyl SulfateHCID 10796Cesium carbonateHCID 312751,4-DioxaneHCID 67264285HCID 67264285, compound

Product 1

HCID 67264350HCID 67264350, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

4-tert-Butoxycarbonylamino-3-hydroxy-12-aza-tricyclo[7.2.1.0*2,7*]dodeca-2(7),3,5-triene-12-carboxylic acid tert-butyl ester (260 mg, 0.67 mmol), dimethyl sulfate (0.13 mL, 1.3 mmol), cesium carbonate (430 mg, 1.3 mmol) and dioxane (3 mL) were stirred together at 90° C. for 20 h. The reaction mixture was then diluted with water (5 mL), extracted with CH2Cl2 (2×5 mL), dried over MgSO4, filtered and concentrated. The resulting residue was purified with silica gel chromatography (0-50% EtOAc in hexanes) to obtain 4-tert-Butoxycarbonylamino-3-methoxy-12-aza-tricyclo[7.2.1.0*2,7*]dodeca-2(7),3,5-triene-12-carboxylic acid tert-butyl ester as a yellow, foamy residue (198 mg, 74%). 1HNMR (400 MHz, CDCl3) δ 7.6 (s, 1H), 7.4 (d, 1H, J=8.0 Hz), 7.1 (d, 1H, J=8.0 Hz), 4.5 (m, 1H), 4.1 (m, 1H), 3.3 (s, 3H), 3.1 (dd, 1H, J=14.4, 4.8 Hz), 2.9 (dd, 1H, J=14.5, 5.0 Hz), 2.7 (dd, 1H, J=17.9, 7.8 Hz), 2.6 (dd, 1H, J=18.4, 10.4 Hz), 2.2 (m, 1H), 1.5-1.4 (m, 19H); MS (m/e) 349 (M−C4H7).

Workup

  1. extractionextracted with CH2Cl2 (2×5 mL)
  2. dry with materialdried over MgSO4
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customThe resulting residue was purified with silica gel chromatography (0-50% EtOAc in hexanes)

Sources & evidence

ORD record
ord-210ccaf26c9a4b6197eed947380c43c0
Source dataset
uspto-grants-2013_10
Patent number
US08552186B2

Reaction notes

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