Hydroxylamine → (+)-3-Acetoxy-4,4-dimethylhept-1-ene

HRID 279406Notes

Reaction equation

HRID 279406 reaction equation
NO.[CH3:3][C:4]([CH3:10])([CH2:7][CH:8]=[CH2:9])[CH:5]=[O:6].C([Zn][CH2:14][CH3:15])C.[C:16](OC(=O)C)(=[O:18])[CH3:17]>CCCCCC.CCOCC.C1(C)C=CC=CC=1>[C:16]([O:6][CH:5]([C:4]([CH3:10])([CH3:3])[CH2:7][CH2:8][CH3:9])[CH:14]=[CH2:15])(=[O:18])[CH3:17]

Participants

8

Reactant 4

HCID 787HydroxylamineHCID 7918Acetic AnhydrideHCID 796362,2-Dimethylpent-4-enalHCID 178418750HCID 178418750, compound

Product 1

HCID 22625127(+)-3-Acetoxy-4,4-dimethylhept-1-eneYield 78%

Reagents, catalysts & solvents 3

HCID 1140TolueneSolventHCID 3283Diethyl EtherSolventHCID 8058HexaneSolvent

Procedure

To a vial containing aminoalcohol 1 (0.05 g, 0.17 mmol) prepared as in Example 1 was added a solution containing 2,2-dimethyl4-pentenal (0.34 g, 90% pure, 2.7 mmol), toluene (3.0 mL), and 1 M diethylzinc in hexane (6.0 mL). After 3 days at room temperature, acetic anhydride (1.2 mL, 13 mmol) was added. After 2 additional days, the mixture was diluted in ether (50 mL) and the reaction was quenched by dropwise addition of half-saturated aqueous ammonium chloride (50 mL). The ether layer was separated and the aqueous layer was further extracted with ether (2×50 mL). The combined ether layers were dried over magnesium sulfate whereupon the solvent was removed at reduced pressure. The residue was purified by flash chromatography on 220-400 mesh silica with 95% hexane and 5% ether as eluant. The product (+)-3-acetoxy-4,4-dimethylhept-1-ene (0.39 g, 78%) was isolated as a colorless liquid by distillation of the solvent at reduced pressure. Anal. for C11H20O2. Calcd: C, 71.70; H, 10.94; found: C, 71.75; H, 10.66. 1H NMR (CDCl3/TMS): δ 0.84 (s+t, 6 H total), 0.87 (s, 3 H), 1.46 (m, 1 H), 1.62 (m, 1 H), 1.89-2.06 (m, 2 H), 2.07 (s, 3 H), 4.71 (dd, 1 H), 4.96-5.05 (m, 2 H), 5.81 (m, 1 H). 13C NMR (CDCl3/TMS): δ 10.96, 21.02, 22.33, 23.12, 37.41, 43.46, 81.41, 117.37, 134.74, 171.11. [α]D25=+14.2, c=2.02 g/100 mL chloroform. Chiral capillary gas chromatographic analysis at 100° C. on Cyclodex B stationary phase (J & W Scientific) indicated that the enantiomeric excess of the product was 98%.

Workup

  1. additionTo a vial containing
  2. additionwas added a solution
  3. customthe reaction was quenched by dropwise addition of half-saturated aqueous ammonium chloride (50 mL)
  4. customThe ether layer was separated
  5. extractionthe aqueous layer was further extracted with ether (2×50 mL)
  6. dry with materialThe combined ether layers were dried over magnesium sulfate whereupon the solvent
  7. customwas removed at reduced pressure
  8. customThe residue was purified by flash chromatography on 220-400 mesh silica with 95% hexane and 5% ether as eluant

Sources & evidence

ORD record
ord-bf5d26d478644066b56c451047d16570
Source dataset
uspto-grants-2002_03
Patent number
US06362344B1

Reaction notes

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