Cesium fluoride → Acetic acid 2-((4aS,4bR,5S,6aS,6bS,9aR,10aS,10bS,12S)-4b,12-difluoro-5-hydroxy-4a,6a-dimethyl-2-oxo-8-phenyl-2,4b,5,6,6a,7,8,9,9a,10,10a,10b,11,12-tetradecahydro-4aH-8-aza-pentaleno[2,1-a]phenanthren-6b-yl)-2-oxo-ethyl ester

HRID 446836

Reaction equation

HRID 446836 reaction equation
Cl.[F:2][C@@:3]12[C@:16]3([CH3:17])[C:11](=[CH:12][C:13](=[O:18])[CH:14]=[CH:15]3)[C@@H:10]([F:19])[CH2:9][C@H:8]1[C@@H:7]1[CH2:20][C@@H:21]3[C@:25]([C:26](=[O:32])[CH2:27][O:28][C:29](=[O:31])[CH3:30])([C@@:6]1([CH3:33])[CH2:5][C@@H:4]2[OH:34])[CH2:24][NH:23][CH2:22]3.FC(F)(F)S(O[C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][C:42]=1[Si](C)(C)C)(=O)=O.[F-].[Cs+]>C(#N)C.O>[F:2][C@@:3]12[C@:16]3([CH3:17])[C:11](=[CH:12][C:13](=[O:18])[CH:14]=[CH:15]3)[C@@H:10]([F:19])[CH2:9][C@H:8]1[C@@H:7]1[CH2:20][C@@H:21]3[C@:25]([C:26](=[O:32])[CH2:27][O:28][C:29](=[O:31])[CH3:30])([C@@:6]1([CH3:33])[CH2:5][C@@H:4]2[OH:34])[CH2:24][N:23]([C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1)[CH2:22]3

Participants

6

Reactant 3

HCID 25953Cesium fluoride2×HCID 33840072-(Trimethylsilyl)phenyl trifluoromethanesulfonateHCID 67353702Acetic acid 2-((4aS,4bR,5S,6aS,6bS,9aR,10aS,10bS,12S)-4b,12-difluoro-5-hydroxy-4a,6a-dimethyl-2-oxo-2,4b,5,6,6a,7,8,9,9a,10,10a,10b,11,12-tetradecahydro-4-aH-8-aza-pentaleno[2,1-a]phenanthren-6b-yl)-2-oxo-ethyl ester hydrochloride

Product 1

HCID 58392743Acetic acid 2-((4aS,4bR,5S,6aS,6bS,9aR,10aS,10bS,12S)-4b,12-difluoro-5-hydroxy-4a,6a-dimethyl-2-oxo-8-phenyl-2,4b,5,6,6a,7,8,9,9a,10,10a,10b,11,12-tetradecahydro-4aH-8-aza-pentaleno[2,1-a]phenanthren-6b-yl)-2-oxo-ethyl esterYield 30.3%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6342AcetonitrileSolvent

Procedure

In a nitrogen atmosphere compound 20 (150 mg, 0.300 mmol) is suspended in Acetonitrile (4 ml). 2-(trimethylsilyl)phenyl trifluoromethanesulfonate (0.146 ml, 0.600 mmol) and CsF (182 mg, 1.200 mmol) are added and the mixture is stirred for 45 minutes at RT. Additional CsF (137 mg, 0.900 mmol) (not dried) is added and the mixture is stirred for 5 hours then it is poured in water. Acetonitrile is evaporated and the reaction mixture is partitioned between water and AcOEt. The organic layer is separated dried over Na2SO4 and concentrated. The crude is purified by silica gel flash chromatography (eluent DCM/MeOH 98/2) affording the title compound (49 mg, 0.091 mmol, 30.3% yield).

Workup

  1. additionis added
  2. stirringthe mixture is stirred for 5 hours
  3. customAcetonitrile is evaporated
  4. customthe reaction mixture is partitioned between water and AcOEt
  5. customThe organic layer is separated
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated
  8. customThe crude is purified by silica gel flash chromatography (eluent DCM/MeOH 98/2)

Sources & evidence

ORD record
ord-56ce27676aca4d0a95002c46b6b45039
Source dataset
uspto-grants-2013_07
Patent number
US08481517B2

Linked notes

Loading…