Acetone → (R)-2,2-diallyl-5-(5-bromo-2-fluoro-phenyl)-4-(2,4-dimethoxy-benzyl)-5-methyl-1,1-dioxo-1lambda6-thiomorpholin-3-one

HRID 920158Notes

Reaction equation

HRID 920158 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([F:29])=[C:6]([C@@:8]2([CH3:28])[N:13]([CH2:14][C:15]3[CH:20]=[CH:19][C:18]([O:21][CH3:22])=[CH:17][C:16]=3[O:23][CH3:24])[C:12](=[O:25])[CH2:11][S:10](=[O:27])(=[O:26])[CH2:9]2)[CH:7]=1.[CH2:30](Br)[CH:31]=[CH2:32].C(=O)([O-])[O-].[K+].[K+].[CH3:40][C:41]([CH3:43])=O>>[CH2:30]([C:11]1([CH2:43][CH:41]=[CH2:40])[S:10](=[O:26])(=[O:27])[CH2:9][C@:8]([C:6]2[CH:7]=[C:2]([Br:1])[CH:3]=[CH:4][C:5]=2[F:29])([CH3:28])[N:13]([CH2:14][C:15]2[CH:20]=[CH:19][C:18]([O:21][CH3:22])=[CH:17][C:16]=2[O:23][CH3:24])[C:12]1=[O:25])[CH:31]=[CH2:32]

Participants

5

Reactant 4

HCID 180AcetoneHCID 7841Allyl bromideHCID 11430Potassium CarbonateHCID 90067087(R)-5-(5-bromo-2-fluoro-phenyl)-4-(2,4-dimethoxy-benzyl)-5-methyl-1,1-dioxo-1lambda6-thiomorpholin-3-one

Product 1

HCID 90067160(R)-2,2-diallyl-5-(5-bromo-2-fluoro-phenyl)-4-(2,4-dimethoxy-benzyl)-5-methyl-1,1-dioxo-1lambda6-thiomorpholin-3-oneYield 53.2%

Procedure

To a solution of (R)-5-(5-bromo-2-fluoro-phenyl)-4-(2,4-dimethoxy-benzyl)-5-methyl-1,1-dioxo-1λ6-thiomorpholin-3-one (1 g, 2.06 mmol, Eq: 1.00) in acetone (8 ml) was added allyl bromide (547 mg, 391 μl, 4.52 mmol, Eq: 2.2), then potassium carbonate (853 mg, 6.17 mmol, Eq: 3.0). The reaction suspension was stirred in a sealed tube for 4 days. Extracted with water and ethyl acetate, the organic layer was separated, dried over Na2SO4, filtered and evaporated to dryness. The residue was chromatographed on 20 g silica gel with 0% to 50% ethyl acetate in heptane to give (R)-2,2-diallyl-5-(5-bromo-2-fluoro-phenyl)-4-(2,4-dimethoxy-benzyl)-5-methyl-1,1-dioxo-1λ6-thiomorpholin-3-one (620 mg, 1.09 mmol, 53.2% yield) as a white foam. MS (ISP): m/z=566.2 [M+H]+ and 568.1 [M+2+H]+.

Workup

  1. extractionExtracted with water and ethyl acetate
  2. customthe organic layer was separated
  3. dry with materialdried over Na2SO4
  4. filtrationfiltered
  5. customevaporated to dryness
  6. customThe residue was chromatographed on 20 g silica gel with 0% to 50% ethyl acetate in heptane

Sources & evidence

ORD record
ord-d708694372ee4b4ebe96fa9e3de4208b
Source dataset
uspto-grants-2016_03
Patent number
US09273042B2

Reaction notes

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