Ammonium Hydroxide → (S)-1-phenylmethoxy-4-penten-2-ol

HRID 1441016Notes

Reaction equation

HRID 1441016 reaction equation
[Cu]C#N.[CH2:4]([O:11][CH2:12][C@H:13]1[CH2:15][O:14]1)[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1.[CH:16]([Mg]Br)=[CH2:17].[NH4+].[Cl-].[NH4+].[OH-]>C1COCC1>[CH2:4]([O:11][CH2:12][C@@H:13]([OH:14])[CH2:15][CH:16]=[CH2:17])[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1

Participants

7

Reactant 5

HCID 14923Ammonium HydroxideHCID 25517Ammonium ChlorideHCID 159746(-)-Benzyl (R)-glycidyl etherHCID 178418507HCID 178418507, compoundHCID 178418546HCID 178418546, compound

Product 1

HCID 11830274(S)-1-phenylmethoxy-4-penten-2-ol

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

Copper(I)cyanide (120 mg, 1.34 mmol) was added to a solution of (R)-(-)-2-(benzyloxymethyl)oxirane (2.4 g, 14.6 mmol) in dry THF (200 ml). This mixture was cooled to -78° C. under argon atmosphere. A solution of vinylmagnesium bromide in THF (26 ml, 1M, 26 mmol) was added slowly to the epoxide solution at -78° C. The reaction mixture was stirred for 5 hours while the reaction temperature was allowed to warm to 0° C. Saturated aqueous NH4Cl and NH4OH were added to the reaction mixture till the reaction mixture became clear. Organic layer was separated and the aqueous layer was extracted with EtOAc (3×50 ml). Combined organic layers were dried over MgSO4 and concentrated. The residue was purified by chromatography (EtOAc/Hexane=1:9) to give 1-benzyloxy-2(S)-hydroxy-4-pentent (2.6 g, 13.5 mmol) NMR (CDCl3): 7.35 (bs, 5H), 5.84 (m, 1H), 5.14 (d, J=11, 1H), 5.11 (d, J=9, 1H), 4.57 (s, 2H), 3.90 (m, 1H), 3.53 (dd, J=3.4, 9.5, 1H), 3.39 (dd, J=7.4, 9.5, 1H) 2.29 (t, J=1.23, 2H).

Workup

  1. temperatureto warm to 0° C
  2. customOrganic layer was separated
  3. extractionthe aqueous layer was extracted with EtOAc (3×50 ml)
  4. dry with materialCombined organic layers were dried over MgSO4
  5. concentrationconcentrated
  6. customThe residue was purified by chromatography (EtOAc/Hexane=1:9)
  7. customto give 1-benzyloxy-2(S)-hydroxy-4-pentent (2.6 g, 13.5 mmol) NMR (CDCl3): 7.35 (bs, 5H), 5.84 (m, 1H), 5.14 (d, J=11, 1H), 5.11 (d, J=9, 1H), 4.57 (s, 2H), 3.90 (m, 1H), 3.53 (dd, J=3.4, 9.5, 1H), 3.39 (dd, J=7.4, 9.5, 1H) 2.29 (t, J=1.23, 2H)

Sources & evidence

ORD record
ord-1fa2048e011046ceae5b93ba2b3f36c8
Source dataset
uspto-grants-1996_03
Patent number
US05502060

Reaction notes

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