Triphenylphosphine → HCID 22136507, compound

HRID 1827486Notes

Reaction equation

HRID 1827486 reaction equation
[C:1]([Si:5]([CH3:13])([CH3:12])[O:6][CH2:7][C:8]#[C:9][CH2:10]O)([CH3:4])([CH3:3])[CH3:2].C1CCN2C(=[N:18]CCC2)CC1.C1C=CC(P(N=[N+]=[N-])(C2C=CC=CC=2)=O)=CC=1.C([O-])(O)=O.[Na+].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[N-]=[N+]=[N-]>C1COCC1>[Si:5]([O:6][CH2:7][C:8]#[C:9][CH2:10][NH2:18])([C:1]([CH3:4])([CH3:3])[CH3:2])([CH3:13])[CH3:12]

Participants

8

Reactant 6

HCID 11776TriphenylphosphineHCID 33558AzideHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 199401P,P-Diphenylphosphinic azideHCID 516892Sodium BicarbonateHCID 54618454-((Tert-butyldimethylsilyl)oxy)but-2-yn-1-ol

Product 1

HCID 22136507HCID 22136507, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To an ice cold, stirred solution of the known 4-(tert-Butyl-dimethyl-silanyloxy)-but-2-yn-1-ol (3.14 g, 15.7 mmol) in THF (50 ml) was added DBU (2.6 ml, 17.4 mmol) and DPPA (3.8 ml, 17.6 mmol). The solution was warmed to room temperature and stirred under an inert atmosphere overnight. The reaction was poured into sat. NaHCO3 and the layers separated. The aqueous layer was re-extracted with EtOAc (2×) and the combined organic layers were dried (Na2SO4), and concentrated under vacuum. Triphenylphosphine (4.61 g, 17.6 mmol) was added to this crude azide dissolved in THF (50 ml), followed by addition of H20 (0.44 ml). The resultant solution was stirred overnight at room temperature, concentrated under reduced pressure and the residue was slurried in a 1:1 mixture of Et2O/pet ether. The solids were removed and the filtrate was concentrated and purified by flash chromatography on silica gel eluting CH2Cl2/MeOH (19:1) to give an amber oil. 1H NMR (CDCl3) δ 4.19 (2H, t, J=1.9 Hz), 3.33 (2H, t, J=1.9 Hz), 0.79 (9H, s), 0.00 (6H, s).

Workup

  1. customthe layers separated
  2. extractionThe aqueous layer was re-extracted with EtOAc (2×)
  3. dry with materialthe combined organic layers were dried (Na2SO4)
  4. concentrationconcentrated under vacuum
  5. additionfollowed by addition of H20 (0.44 ml)
  6. concentrationconcentrated under reduced pressure
  7. additionthe residue was slurried in a 1:1 mixture of Et2O/pet ether
  8. customThe solids were removed
  9. concentrationthe filtrate was concentrated
  10. custompurified by flash chromatography on silica gel
  11. washeluting CH2Cl2/MeOH (19:1)
  12. customto give an amber oil

Sources & evidence

ORD record
ord-80594267981c498489dc24e21489af5b
Source dataset
uspto-grants-2006_05
Patent number
US07053107B2

Reaction notes

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