Diethyl Ether → (5-Bromo-2-methoxyphenyl)(2,6-difluoro-5-(tributylstannyl)pyridin-3-yl)methanone

HRID 335904Notes

Reaction equation

HRID 335904 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([O:38][CH3:39])=[C:6]([CH:8]([O:30][Si](C(C)(C)C)(C)C)[C:9]2[C:10]([F:29])=[N:11][C:12]([F:28])=[C:13]([Sn:15]([CH2:24][CH2:25][CH2:26][CH3:27])([CH2:20][CH2:21][CH2:22][CH3:23])[CH2:16][CH2:17][CH2:18][CH3:19])[CH:14]=2)[CH:7]=1.[F-].C([N+](CCCC)(CCCC)CCCC)CCC.C(OCC)C.[Cl-].[NH4+]>C1COCC1.C(Cl)Cl.O.[Ru]([O-])(=O)(=O)=O.C([N+](CCC)(CCC)CCC)CC>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([O:38][CH3:39])=[C:6]([C:8]([C:9]2[C:10]([F:29])=[N:11][C:12]([F:28])=[C:13]([Sn:15]([CH2:16][CH2:17][CH2:18][CH3:19])([CH2:20][CH2:21][CH2:22][CH3:23])[CH2:24][CH2:25][CH2:26][CH3:27])[CH:14]=2)=[O:30])[CH:7]=1

Participants

9

Reactant 4

HCID 3283Diethyl EtherHCID 25517Ammonium ChlorideHCID 2724141Tetrabutylammonium FluorideHCID 673829473-((5-Bromo-2-methoxyphenyl)(tert-butyldimethylsilyloxy)methyl)-2,6-difluoro-5-(tributylstannyl)pyridine

Product 1

HCID 67383097(5-Bromo-2-methoxyphenyl)(2,6-difluoro-5-(tributylstannyl)pyridin-3-yl)methanone

Reagents, catalysts & solvents 4

HCID 178419074HCID 178419074, compoundCatalystHCID 962WaterSolvent2×HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

3-((5-Bromo-2-methoxyphenyl)(tert-butyldimethylsilyloxy)methyl)-2,6-difluoro-5-(tributylstannyl)pyridine (1.17 g, 1.595 mmol) was dissolved in dry THF (10 mL). Tetrabutylammonium fluoride (2.2 mL, 2.200 mmol) was added and the reaction stirred for 5 minutes. Water (100 mL), diethyl ether (100 mL) and saturated ammonium chloride (10 mL) were added. The phases were mixed and separated and the organic dried with magnesium sulfate before evaporating to dryness under reduced pressure. The crude alcohol was dissolved in DCM (50 mL) and treated with 4-methylmorpholine n-oxide (0.467 g, 3.99 mmol) followed by tetrapropylammonium perruthenate (0.056 g, 0.160 mmol). The dark yellow solution was stirred for 15 minutes until it turned black. The solution was diluted with DCM (50 mL) and water (100 mL). The phases were mixed, filtered through a pad of celite and separated and the organic dried with magnesium sulfate before evaporating to dryness under reduced pressure. The crude was purified using silica chromatography (hexane to DCM gradient) to give (5-bromo-2-methoxyphenyl)(2,6-difluoro-5-(tributylstannyl)pyridin-3-yl)methanone.

Workup

  1. additionThe phases were mixed
  2. customseparated
  3. dry with materialthe organic dried with magnesium sulfate
  4. custombefore evaporating to dryness under reduced pressure
  5. dissolutionThe crude alcohol was dissolved in DCM (50 mL)
  6. stirringThe dark yellow solution was stirred for 15 minutes until it
  7. additionThe phases were mixed
  8. filtrationfiltered through a pad of celite
  9. customseparated
  10. dry with materialthe organic dried with magnesium sulfate
  11. custombefore evaporating to dryness under reduced pressure
  12. customThe crude was purified

Sources & evidence

ORD record
ord-e4a9d23d2b69414c880dc8e7ee67759b
Source dataset
uspto-grants-2014_11
Patent number
US08883782B2

Reaction notes

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