Allyl bromide → HCID 68003986, compound

HRID 1408877Notes

Reaction equation

HRID 1408877 reaction equation
Br[C:2]1[CH:3]=[C:4]([F:21])[C:5]([N:8]2[CH2:13][CH2:12][N:11]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH2:10][CH2:9]2)=[N:6][CH:7]=1.[CH2:22](Br)[CH:23]=[CH2:24]>C1COCC1.[Cu]I>[CH2:24]([C:2]1[CH:3]=[C:4]([F:21])[C:5]([N:8]2[CH2:13][CH2:12][N:11]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH2:10][CH2:9]2)=[N:6][CH:7]=1)[CH:23]=[CH2:22]

Participants

5

Reactant 2

HCID 7841Allyl bromideHCID 68004132HCID 68004132, compound

Product 1

HCID 68003986HCID 68003986, compoundYield 69%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
0 °C

Procedure

In a dry 3-necked flask flushed with argon containing a solution of 11 (6.86 g, 19.05 mmol) in THF (40 mL) at 0° C. was added a 1.3 M THF solution of isopropyl magnesium chloride lithium chloride complex (19.1 mL, 24.8 mmol) over 10 min. After 10 additional minutes of stirring at 0° C., CuI (0.73 g, 3.81 mmol) was added, the mixture was stirred for 10 minutes at 0° C. and then a solution of allyl bromide (3.3 mL, 38.1 mmol) in THF (4.0 mL) was added at 0° C. over 10 min. After further stirring for 1 h at 0° C., the reaction was quenched with 10% citric acid and extracted with ethyl acetate (100 mL×2). The organic layers were combined which was washed with brine, dried over Na2SO4, and concentrated. The obtained residue was chromatographed on silica gel eluted with hexane and 10% ethyl acetate in hexanes to afford 4.22 g of 12 (69%) as a colorless oil which was used directly for the next step. LC/MS (M+1) 322.

Workup

  1. stirringthe mixture was stirred for 10 minutes at 0° C.
  2. stirringAfter further stirring for 1 h at 0° C.
  3. customthe reaction was quenched with 10% citric acid
  4. extractionextracted with ethyl acetate (100 mL×2)
  5. washwas washed with brine
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated
  8. customThe obtained residue was chromatographed on silica gel
  9. washeluted with hexane and 10% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-64f7c1ad40dd43a6a147c7b9ad3427c7
Source dataset
uspto-grants-2014_12
Patent number
US08921373B2

Reaction notes

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