Allyl bromide → HCID 68004032, compound

HRID 1408880Notes

Reaction equation

HRID 1408880 reaction equation
Br[C:2]1[CH:3]=[C:4]([F:22])[C:5]([C:8]2([F:21])[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.[Cl-].[Li+].[CH:25]([Mg]Cl)([CH3:27])[CH3:26].C(Br)C=C>C1COCC1.[Cu]I>[CH2:27]([C:2]1[CH:3]=[C:4]([F:22])[C:5]([C:8]2([F:21])[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:25]=[CH2:26]

Participants

6

Reactant 3

HCID 7841Allyl bromideHCID 68004104HCID 68004104, compoundHCID 178461733HCID 178461733, compound

Product 1

HCID 68004032HCID 68004032, compoundYield 84%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

In a dry 3-necked flask flushed with argon containing a solution of 23 (3.77 g, 10.0 mmol) in THF (50 mL) at 0° C. was added isopropyl magnesium chloride lithium chloride complex (1.3 M in THF, 10 mL, 13 mmol) over 10 min. After additional 10 min of stirring at 0° C., CuI (0.2 eq, 0.38 g) was added, the mixture was stirred for 10 minutes at 0° C. and then a solution of allyl bromide (1.73 mL, 20 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 EtOAc/hexane (0-10%) to afford 2.84 g (84%) of 24 as a colorless oil. NMR (CDCl3) δ 1.48 (9 H, s), 2.21 (4 H, m), 3.28 (2 H, m), 3.41 (2 H, d, J=6.16 Hz), 4.05 (2 H, m), 5.92 (1 H, m), 7.26 (1 H, dd, J=1.56, 12.08 Hz); LC/MS (M+1) 339.

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 EtOAc/hexane (0-10%)

Sources & evidence

ORD record
ord-b07860a989a1479294cd90862881f027
Source dataset
uspto-grants-2014_12
Patent number
US08921373B2

Reaction notes

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