Ammonium Chloride → (3S)-(E)-4-fluoro-3-hydroxy-1-phenyl-1-butene

HRID 1042965Notes

Reaction equation

HRID 1042965 reaction equation
[F:1][C:2]1([C@@H:15]([OH:25])[CH:16]=[C:17]([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)C)S(=O)(=O)C2C=CC=CC=2S1(=O)=O.[I-].[Sm+2].[I-].O1CCCC1.[Cl-].[NH4+]>CO>[F:1][CH2:2][C@@H:15]([OH:25])/[CH:16]=[CH:17]/[C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1

Participants

5

Reactant 3

HCID 25517Ammonium ChlorideHCID 866607092-fluoro-2-[(1S)-1-hydroxy-3-phenyl-2-butenyl]-1,3-benzodithiol 1,1,3,3-tetraoxideHCID 178420694Diiodosamarium;oxolane

Product 1

HCID 58581808(3S)-(E)-4-fluoro-3-hydroxy-1-phenyl-1-butene

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A 5 ml round-bottomed flask provided with a stirrer was charged with the 2-fluoro-2-[(1S)-1-hydroxy-3-phenyl-2-butenyl]-1,3-benzodithiol 1,1,3,3-tetraoxide (41.2 mg, 0.11 mmol, 91% ee) prepared in Example 11 and MeOH (2.0 ml). The resultant mixture was cooled to 40° C. Samarium(II) iodide/tetrahydrofuran (0.1 M, 6.7 ml) was slowly added dropwise, and the mixture was stirred for 1 hour. Then, a saturated ammonium chloride aqueous solution was added. The aqueous layer was extracted with dichloromethane. A sodium thiosulfate aqueous solution was added to the organic layer, and the organic layer was extracted. Then, the organic layer was dried over anhydrous magnesium sulfate. The solvent was removed by distillation using an evaporator, and then the product was purified by silica gel column chromatography (dichloromethane:methanol=95:5) to obtain 15.0 mg (81%, 90% ee) of the target (3S)-(E)-4-fluoro-3-hydroxy-1-phenyl-1-butene.

Workup

  1. customA 5 ml round-bottomed flask provided with a stirrer
  2. extractionThe aqueous layer was extracted with dichloromethane
  3. additionA sodium thiosulfate aqueous solution was added to the organic layer
  4. extractionthe organic layer was extracted
  5. dry with materialThen, the organic layer was dried over anhydrous magnesium sulfate
  6. customThe solvent was removed by distillation
  7. customan evaporator
  8. customthe product was purified by silica gel column chromatography (dichloromethane:methanol=95:5)

Sources & evidence

ORD record
ord-842fe28d1af44d6d8eda2c621b6b7bd6
Source dataset
uspto-grants-2013_10
Patent number
US08558012B2

Reaction notes

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