tert-Butyl hydroperoxide → (3S,5S)-9-(tetrahydro-pyran-2-yloxy)-non-1-en-7-yne-3,5-diol

HRID 581619Notes

Reaction equation

HRID 581619 reaction equation
[O:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]1[O:7][CH2:8][C:9]#[C:10][CH2:11][C@H:12]([OH:21])[CH2:13]/[CH:14]=[CH:15]\[CH2:16][Si](C)(C)C.C([O:26]O)(C)(C)C.COP(OC)OC>C1(C)C=CC=CC=1>[O:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]1[O:7][CH2:8][C:9]#[C:10][CH2:11][C@H:12]([OH:21])[CH2:13][C@H:14]([OH:26])[CH:15]=[CH2:16]

Participants

5

Reactant 3

HCID 6410tert-Butyl hydroperoxideHCID 8472Trimethyl phosphiteHCID 70003429(Z)-(5R)-9-(tetrahydro-pyran-2-yloxy)-1-trimethylsilanyl-non-2-en-7-yn-5-ol

Product 1

HCID 57143448(3S,5S)-9-(tetrahydro-pyran-2-yloxy)-non-1-en-7-yne-3,5-diol

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

17.83 g (57.4 mmol) of (Z)-(5R)-9-(tetrahydro-pyran-2-yloxy)-1-trimethylsilanyl-non-2-en-7-yn-5-ol was dissolved in 210 ml of abs. toluene. At -15°, 30.6 ml t-butyl-hydroperoxide (3M, toluene) was added, followed by 761 mg (5 mol%) of vanadium-oxyacetylacetonate. The temperature was then rised within 16 h to 220. TLC indicated the disappearance of starting olefin. While cooling in an ice bath, 13.5 ml (115 mmol) of trimethylphosphite was added in order to destroy the excess of hydroperoxide. 90 minutes later, a solution of 39.8 g of dry TBAF in 125 ml of THF was added and the reaction mixture kept for 90 minutes at RT. The homogeneous solution was then poured onto crushed ice, extracted with AcOEt, washed with water, dried over sodium sulfate and evaporated to dryness. Flash chromatography (SiO2, hexane/AcOEt=6/4) yielded 10.40 g of (3S,5S)-9-(tetrahydro-pyran-2-yloxy)-non-1-en-7-yne-3,5-diol as slightly yellow oil (1:1 epimeric mixture).

Workup

  1. temperatureWhile cooling in an ice bath
  2. customto destroy the excess of hydroperoxide
  3. addition90 minutes later, a solution of 39.8 g of dry TBAF in 125 ml of THF was added
  4. waitthe reaction mixture kept for 90 minutes at RT
  5. additionThe homogeneous solution was then poured
  6. customonto crushed ice
  7. extractionextracted with AcOEt
  8. washwashed with water
  9. dry with materialdried over sodium sulfate
  10. customevaporated to dryness

Sources & evidence

ORD record
ord-3957d5e5e41646c1bc49d3c5ef1a5f5c
Source dataset
uspto-grants-1999_07
Patent number
US05919986

Reaction notes

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