Tetrabutylammonium Fluoride → (1S, 4R, 6S, 14S, 18R)-[7-cis-4-Cyclopropanesulfonylaminocarbonyl-12-cyclopropyl-18-hydroxy-2,15-dioxo-3,12,16-triaza-tricyclo[14.3.0.04,6]nonadec-7-en-14-yl]carbamic acid, tert-butyl ester

HRID 500415Notes

Reaction equation

HRID 500415 reaction equation
[CH:1]1([S:4]([NH:7][C:8]([C@@:10]23[CH2:28][C@H:27]2[CH:26]=[CH:25][CH2:24][CH2:23][CH2:22][N:21]([CH:29]2[CH2:31][CH2:30]2)[CH2:20][C@H:19]([NH:32][C:33](=[O:39])[O:34][C:35]([CH3:38])([CH3:37])[CH3:36])[C:18](=[O:40])[N:17]2[C@@H:13]([CH2:14][C@@H:15]([O:41][Si](C(C)(C)C)(C)C)[CH2:16]2)[C:12](=[O:49])[NH:11]3)=[O:9])(=[O:6])=[O:5])[CH2:3][CH2:2]1.[F-].C([N+](CCCC)(CCCC)CCCC)CCC>C1COCC1>[CH:1]1([S:4]([NH:7][C:8]([C@@:10]23[CH2:28][C@H:27]2[CH:26]=[CH:25][CH2:24][CH2:23][CH2:22][N:21]([CH:29]2[CH2:30][CH2:31]2)[CH2:20][C@H:19]([NH:32][C:33](=[O:39])[O:34][C:35]([CH3:36])([CH3:37])[CH3:38])[C:18](=[O:40])[N:17]2[C@@H:13]([CH2:14][C@@H:15]([OH:41])[CH2:16]2)[C:12](=[O:49])[NH:11]3)=[O:9])(=[O:5])=[O:6])[CH2:3][CH2:2]1

Participants

4

Reactant 2

HCID 2724141Tetrabutylammonium FluorideHCID 68252750(1S,4R,6S,14S,18R)-[7-cis-4-Cyclopropanesulfonylaminocarbonyl-12-cyclopropyl-18-(tert-butyldimethylsilyloxy)-2,15-dioxo-3,12,16-triaza-tricyclo[14.3.0.04,6]nonadec-7-en-14-yl]carbamic acid, tert-butyl ester

Product 1

HCID 70303909(1S, 4R, 6S, 14S, 18R)-[7-cis-4-Cyclopropanesulfonylaminocarbonyl-12-cyclopropyl-18-hydroxy-2,15-dioxo-3,12,16-triaza-tricyclo[14.3.0.04,6]nonadec-7-en-14-yl]carbamic acid, tert-butyl esterYield 95%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a mixture of compound (1S,4R,6S,14S,18R)-[7-cis-4-Cyclopropanesulfonylaminocarbonyl-12-cyclopropyl-18-(tert-butyldimethylsilyloxy)-2,15-dioxo-3,12,16-triaza-tricyclo[14.3.0.04,6]nonadec-7-en-14-yl]carbamic acid, tert-butyl ester (250 mg, 0.35 mmoL) in 15 mL of THF was added tetrabutylammonium fluoride (129 mg, 0.46 mmoL). The mixture was stirred at rt for 18 h. THF was removed by rotary evaporation, and the residue was partitioned between ethyl acetate and water. The organic phase was dried (MgSO4) and concentrated in vacuo to give the crude product. Purification by triturating with hexane provided 200 mg (94%) of (1S,4R,6S,14S,18R)-[7-cis-4-Cyclopropanesulfonylaminocarbonyl-12-cyclopropyl-18-hydroxy-2,15-dioxo-3,12,16-triaza-tricyclo[14.3.0.04,6]nonadec-7-en-14-yl]carbamic acid, tert-butyl ester as a white solid: LC-MS (retention time: 2.32 min), MS m/z 610 (M++1). (Phenomenex 10 μm C18HPLC column: 3.0×50 mm length. Gradient: 100% Solvent A/0% Solvent B to 0% Solvent A/100% Solvent B. Gradient time: 3 min. Hold time: 1 min. Flow rate: 4 mL/min. Detector Wavelength: 220 nM. Solvent A: 10% MeOH/90% H2O/0.1% TFA. Solvent B: 10% H2O/90% MeOH/0.1% TFA.) (Retention time: 2.32 min), MS m/z 610 (M++1).

Workup

  1. customTHF was removed by rotary evaporation
  2. customthe residue was partitioned between ethyl acetate and water
  3. dry with materialThe organic phase was dried (MgSO4)
  4. concentrationconcentrated in vacuo
  5. customto give the crude product
  6. customPurification
  7. customby triturating with hexane

Sources & evidence

ORD record
ord-f813618636f24ffaa49b8ab52817cabb
Source dataset
uspto-grants-2010_08
Patent number
US07772183B2

Reaction notes

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