Cesium carbonate → HCID 86640730, compound

HRID 335759Notes

Reaction equation

HRID 335759 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]([O:25][CH3:26])([CH3:24])[CH3:23])[CH:18]=3)[O:13][C:12]3[C:7]2=[CH:8][C:9]([OH:27])=[CH:10][CH:11]=3)[N:6]=1.C(=O)([O-])[O-].[Cs+].[Cs+].[F:34][C:35]([F:50])([C:46]([F:49])([F:48])[F:47])[C:36]([F:45])([F:44])[C:37]([F:43])([F:42])[S:38](F)(=[O:40])=[O:39]>CN(C=O)C>[F:43][C:37]([F:42])([S:38]([O:27][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]([O:25][CH3:26])([CH3:24])[CH3:23])[CH:18]=3)[O:13][C:12]2=[CH:11][CH:10]=1)(=[O:40])=[O:39])[C:36]([F:44])([F:45])[C:35]([F:50])([F:34])[C:46]([F:49])([F:48])[F:47]

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 67814Perfluoro-1-butanesulfonyl fluorideHCID 67246263HCID 67246263, compound

Product 1

HCID 86640730HCID 86640730, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A 25-mL flask was charged with (R)-2′-amino-3-(3-methoxy-3-methylbut-1-ynyl)-5′H-spiro[chromeno[2,3-b]pyridine-5,4′-oxazol]-7-ol (577.53 mg, 1.581 mmol), cesium carbonate (566 mg, 1.739 mmol), and DMF (7903 μL). The resulting mixture was stirred for 10 min, then the vial was submerged in an ice-bath for 10 min. nonafluorobutanesulfonyl fluoride (306 μL, 1.739 mmol) was added dropwise over 2 minutes. The mixture was stirred for 2 hours, then quenched with saturated aqueous ammonium chloride (10 mL), and partitioned between water (15 mL) and EtOAc (15 mL). The layers were separated, and the aqueous layer was extracted with EtOAc (15 mL). The combined organic layers 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 0-50% of a 90:10 mixture of DCM/MeOH in DCM to give (R)-2′-amino-3-(3-methoxy-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 2 hours
  3. customquenched with saturated aqueous ammonium chloride (10 mL)
  4. custompartitioned between water (15 mL) and EtOAc (15 mL)
  5. customThe layers were separated
  6. extractionthe aqueous layer was extracted with EtOAc (15 mL)
  7. washThe combined organic layers were washed with brine
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. customevaporated
  11. customThe residue was purified by chromatography on an 80-g Redi-Sep column
  12. washeluting with 0-50% of a 90:10 mixture of DCM/MeOH in DCM

Sources & evidence

ORD record
ord-d8f5d015b13d4600a11dd14c6206c370
Source dataset
uspto-grants-2014_11
Patent number
US08883782B2

Reaction notes

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