Boron trifluoride etherate → HCID 21835229, compound

HRID 1741287Notes

Reaction equation

HRID 1741287 reaction equation
[CH2:1]([Li])[CH2:2][CH2:3][CH3:4].[CH2:6]([Si:8]([C:13]#[CH:14])([CH2:11][CH3:12])[CH2:9][CH3:10])[CH3:7].B(F)(F)F.CC[O:21][CH2:22][CH3:23].[CH2:24]([N:26](CC)CC)[CH3:25].[C:31]([O:35][C:36]([O:38]C([O-])=O)=O)([CH3:34])([CH3:33])[CH3:32]>C1COCC1>[C:31]([O:35][C:36]([N:26]1[CH2:24][CH2:25][CH:3]([CH2:4][CH:22]([OH:21])[CH2:23][C:14]#[C:13][Si:8]([CH2:11][CH3:12])([CH2:9][CH3:10])[CH2:6][CH3:7])[CH2:2][CH2:1]1)=[O:38])([CH3:32])([CH3:33])[CH3:34]

Participants

7

Reactant 5

HCID 8000Boron trifluoride etherateHCID 8471TriethylamineHCID 637947(Triethylsilyl)acetyleneHCID 22064466Tert-butyldicarbonateHCID 178418339Butyllithium

Product 1

HCID 21835229HCID 21835229, compoundYield 49%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

A dry flask under N2 was charged with THF (50 ml) and n-butyllithium (13 ml, 0.021 mol, 1.6 M solution in hexanes) and cooled to -78° C. Triethylsilylacetylene (3.0 ml, 0.021 mol) was added dropwise and the reaction stirred for 0.5 h. Distilled boron trifluoride etherate (3.03 ml, 0.025 mol) was then added and the reaction stirred at -78° C. for a further 10 min. The epoxide (step a) was then added as a solution in THF (20 ml) and the reaction stirred for 0.75 h. The reaction was quenched by the addition of saturated NH4Cl and extracted into ethyl acetate. The organic layer was dried over MgSO4 and evaporated in vacuo. The residue was taken up in dioxane:water (1:1, 100 ml) and triethylamine (2.0 ml, 0.0145 mol) added followed by tert-butyldicarbonate (3.0 g, 0.0145 mol). The reaction was stirred for 1h, the dioxane evaporated and the residue partitioned between ethyl acetate and saturated NH4Cl. The organic layer was collected, dried over MgSO4 and evaporated. The residue was chromatographed on silica eluting with ethyl acetate:hexanes (1:9→2:8) to obtain the alcohol as a colourless oil (2.4 g, 49%). 1H NMR (250 MHz, CDCl3) δ 0.58 (6H, q), 0.95 (9H, t), 1.08-1.16 (3H, m), 1.45 (9H, s), 1.59-1.78 (4H, m), 2.35 (1H, dd), 2.47 (1H, dd), 2.73 (2H, t), 4.12 (3H, m).

Workup

  1. stirringthe reaction stirred at -78° C. for a further 10 min
  2. stirringthe reaction stirred for 0.75 h
  3. customThe reaction was quenched by the addition of saturated NH4Cl
  4. extractionextracted into ethyl acetate
  5. dry with materialThe organic layer was dried over MgSO4
  6. customevaporated in vacuo
  7. customthe dioxane evaporated
  8. customthe residue partitioned between ethyl acetate and saturated NH4Cl
  9. customThe organic layer was collected
  10. dry with materialdried over MgSO4
  11. customevaporated
  12. customThe residue was chromatographed on silica eluting with ethyl acetate:hexanes (1:9→2:8)

Sources & evidence

ORD record
ord-6acc850c99294cc89a68c465119a21ec
Source dataset
uspto-grants-1999_10
Patent number
US05973156

Reaction notes

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