Sodium Azide → (1R)-2-{[tert-butyl(dimethyl)silyl]oxy}-1-tetrahydro-2H-pyran-4-ylethyl methanesulfonate

HRID 549160Notes

Reaction equation

HRID 549160 reaction equation
[CH3:1][S:2]([O:5][C@H:6]([CH:16]1[CH2:21][CH2:20][O:19][CH2:18][CH2:17]1)[CH2:7][O:8][Si:9]([C:12]([CH3:15])([CH3:14])[CH3:13])([CH3:11])[CH3:10])(=[O:4])=[O:3].[N-:22]=[N+:23]=[N-:24].[Na+]>CN(C=O)C>[N:22]([C@@H:6]([CH:16]1[CH2:21][CH2:20][O:19][CH2:18][CH2:17]1)[CH2:7][O:8][Si:9]([C:12]([CH3:15])([CH3:14])[CH3:13])([CH3:11])[CH3:10])=[N+:23]=[N-:24].[CH3:1][S:2]([O:5][C@H:6]([CH:16]1[CH2:17][CH2:18][O:19][CH2:20][CH2:21]1)[CH2:7][O:8][Si:9]([C:12]([CH3:15])([CH3:14])[CH3:13])([CH3:11])[CH3:10])(=[O:3])=[O:4]

Participants

5

Reactant 2

HCID 33557Sodium AzideHCID 86624125(1R)-2-{[tert-butyl(dimethyl)silyl]oxy}-1-tetrahydro-2H-pyran-4-ylethyl methanesulfonate

Product 2

HCID 86624125(1R)-2-{[tert-butyl(dimethyl)silyl]oxy}-1-tetrahydro-2H-pyran-4-ylethyl methanesulfonateHCID 86624126{[(2S)-2-azido-2-tetrahydro-2H-pyran-4-ylethyl]oxy}(tert-butyl)dimethylsilane

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
60 °C

Procedure

A solution of (1R)-2-{[tert-butyl(dimethyl)silyl]oxy}-1-tetrahydro-2H-pyran-4-ylethyl methanesulfonate (4.29 g, 12.7 mmol) in 40 mL of DMF was treated with sodium azide (1.00 g, 15.2 mmol) and the mixture was heated to 60° C. for 12 hours and then to 80° C. for 8 hours. The reaction mixture was concentrated under reduced pressure and the resulting material was dissolved in 50 mL of ethyl acetate and washed successively with H2O (3×25 mL) and brine (25 mL). The organic layer was dried over Na2SO4, filtered and concentrated under reduced pressure. Chromatography (SiO2, 10-25% ethyl acetate/hexanes) gave 1.60 g of {[(2S)-2-azido-2-tetrahydro-2H-pyran-4-ylethyl]oxy}(tert-butyl)dimethylsilane as a colorless oil and 1.50 g of recovered (1R)-2-{[tert-butyl(dimethyl)silyl]oxy}-1-tetrahydro-2H-pyran-4-ylethyl methanesulfonate. The recovered starting material was again subjected to the reaction conditions to afford an additional 0.59 g of product.

Workup

  1. concentrationThe reaction mixture was concentrated under reduced pressure
  2. dissolutionthe resulting material was dissolved in 50 mL of ethyl acetate
  3. washwashed successively with H2O (3×25 mL) and brine (25 mL)
  4. dry with materialThe organic layer was dried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-905a00523d9f4237b690b04c0558fef8
Source dataset
uspto-grants-2011_05
Patent number
US07943609B2

Reaction notes

Loading…