Dimethylformamide → (S)-2'-amino-3-(3-hydroxy-3-methylbut-1-ynyl)-5'H-spiro[chromeno[2,3-b]pyridine-5,4'-oxazole]-7-yl 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate

HRID 335761Notes

Reaction equation

HRID 335761 reaction equation
[NH2:1][C:2]1[O:3][CH2:4][C@:5]2([C:19]3[C:14](=[N:15][CH:16]=[C:17]([C:20]#[C:21][C:22]([OH:25])([CH3:24])[CH3:23])[CH:18]=3)[O:13][C:12]3[C:7]2=[CH:8][C:9]([OH:26])=[CH:10][CH:11]=3)[N:6]=1.C(=O)([O-])[O-].[Cs+].[Cs+].CN(C=O)C.[F:38][C:39]([F:54])([C:50]([F:53])([F:52])[F:51])[C:40]([F:49])([F:48])[C:41]([F:47])([F:46])[S:42](F)(=[O:44])=[O:43]>O.[Cl-].[Na+].O>[F:47][C:41]([F:46])([S:42]([O:26][C:9]1[CH:8]=[C:7]2[C@@:5]3([CH2:4][O:3][C:2]([NH2:1])=[N:6]3)[C:19]3[C:14](=[N:15][CH:16]=[C:17]([C:20]#[C:21][C:22]([OH:25])([CH3:23])[CH3:24])[CH:18]=3)[O:13][C:12]2=[CH:11][CH:10]=1)(=[O:44])=[O:43])[C:40]([F:48])([F:49])[C:39]([F:54])([F:38])[C:50]([F:53])([F:52])[F:51]

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 10796Cesium carbonateHCID 67814Perfluoro-1-butanesulfonyl fluorideHCID 67240963(S)-2'-amino-3-(3-hydroxy-3-methylbut-1-ynyl)-5'H-spiro[chromeno[2,3-b]pyridine-5,4'-oxazol]-7-ol

Product 1

HCID 86640731(S)-2'-amino-3-(3-hydroxy-3-methylbut-1-ynyl)-5'H-spiro[chromeno[2,3-b]pyridine-5,4'-oxazole]-7-yl 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

A 25-mL flask was charged with (S)-2′-amino-3-(3-hydroxy-3-methylbut-1-ynyl)-5′H-spiro[chromeno[2,3-b]pyridine-5,4′-oxazol]-7-ol (437.24 mg, 1.244 mmol), cesium carbonate (446 mg, 1.369 mmol), and DMF (6222 μL). The resulting mixture was stirred for 10 min, then the vial was submerged in an ice-bath for 10 min. nonafluorobutanesulfonyl fluoride (241 μL, 1.369 mmol) was added dropwise over 1 min. The mixture was stirred for 3 hours before being diluted with water (20 mL) and a small amount of brine. This mixture was extracted with EtOAc (2×20 mL). The combined organic extracts were washed with brine, dried over sodium sulfate, filtered, and evaporated. The residue was purified by chromatography on an 80-g Redi-Sep column, eluting with 0-60% of a 90:10 mixture of DCM/MeOH in DCM to give (S)-2′-amino-3-(3-hydroxy-3-methylbut-1-ynyl)-5′H-spiro[chromeno[2,3-b]pyridine-5,4′-oxazole]-7-yl 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate as a white solid.

Workup

  1. waitthe vial was submerged in an ice-bath for 10 min.
  2. stirringThe mixture was stirred for 3 hours
  3. extractionThis mixture was extracted with EtOAc (2×20 mL)
  4. washThe combined organic extracts were washed with brine
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. customevaporated
  8. customThe residue was purified by chromatography on an 80-g Redi-Sep column
  9. washeluting with 0-60% of a 90:10 mixture of DCM/MeOH in DCM

Sources & evidence

ORD record
ord-e246de92e6444192b75ecd1e026aea64
Source dataset
uspto-grants-2014_11
Patent number
US08883782B2

Reaction notes

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