Triethylamine → (6S,11S)-9-hydroxy-2,6,11,15-tetramethylhexadeca-2,14-dien-8-one

HRID 713602Notes

Reaction equation

HRID 713602 reaction equation
[CH3:1][C@H:2]([CH2:9][CH:10]=[O:11])[CH2:3][CH2:4][CH:5]=[C:6]([CH3:8])[CH3:7].C(N([CH2:17][CH3:18])CC)C.C([O:22][CH2:23][CH3:24])(=O)C>C(O)C.[Br-].C([N+]1C(C)=C(CCO)SC=1)C>[OH:11][CH:10]([CH2:9][C@@H:2]([CH3:1])[CH2:3][CH2:4][CH:5]=[C:6]([CH3:7])[CH3:8])[C:23](=[O:22])[CH2:24][C@@H:17]([CH3:18])[CH2:5][CH2:4][CH:3]=[C:2]([CH3:9])[CH3:1]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 8857Ethyl AcetateHCID 443157(S)-(-)-Citronellal

Product 1

HCID 58098929(6S,11S)-9-hydroxy-2,6,11,15-tetramethylhexadeca-2,14-dien-8-oneYield 75%

Reagents, catalysts & solvents 2

HCID 99649233-Ethyl-5-(2-hydroxyethyl)-4-methylthiazolium bromideCatalystHCID 702EthanolSolvent

Procedure

To a 250 mL of two-necked round-bottom (RB) flask containing (−) citronellal (25.0 g, 163 mmol) in 50 mL of ethanol under argon was added the catalyst of 3-ethyl-5-(2-hydroxyethyl)-4-methylthiazolium bromide (4.1 g, 16.3 mmol) and triethylamine (17.0 mL, 120 mmol). The mixture was then heated to reflux over night. After removal of the solvent under reduced pressure, the resulted mixture was poured into 100 mL of water and extracted by ethyl ether (3×60 mL). The combined organic layer was dried over anhydrous MgSO4 and concentrated under vacuum. The residue was purified by flash chromatography on silica gel (hexane:ethyl acetate=20:1, v/v) to afford 18.5 g of product as a colorless oil (yield: 75%). 1H NMR (400 MHz, CDCl3) δ 5.08 (m, 2H), 4.15 (m, 1H), 3.47 (dd, 1H, J=5.04 Hz), 2.40 (m, 1H), 2.2 (m, 1H), 1.9-2.1 (m, 6H), 1.60 (d, 12H), 1.1-1.3 (m, 4H), 0.8-1.0 (m, 6H). 13C NMR (400 MHz, CDCl3) δ 212.63, 131.63, 131.30, 124.52, 124.40, 124.00, 75.59, 74.70, 45.16, 45.15, 41.15, 41.00, 37.95, 36.85, 36.83, 35.56, 29.36, 29.04, 28.92, 28.81, 25.65, 25.42, 25.39, 25.36, 25.22, 20.29, 19.82, 19.65, 18.46, 17.60.

Workup

  1. temperatureThe mixture was then heated
  2. temperatureto reflux over night
  3. customAfter removal of the solvent under reduced pressure
  4. additionthe resulted mixture was poured into 100 mL of water
  5. extractionextracted by ethyl ether (3×60 mL)
  6. dry with materialThe combined organic layer was dried over anhydrous MgSO4
  7. concentrationconcentrated under vacuum
  8. customThe residue was purified by flash chromatography on silica gel (hexane

Sources & evidence

ORD record
ord-aef4402aff2147cd95475880ab02d601
Source dataset
uspto-grants-2015_11
Patent number
US09184390B2

Reaction notes

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