Dimethyl Sulfoxide → tert-Butyl (3-((tert-butyldimethylsilyl)oxy)-2-oxopropyl)carbamate

HRID 623370Notes

Reaction equation

HRID 623370 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[C:11]([Si:15]([CH3:30])([CH3:29])[O:16][CH2:17][CH:18]([OH:28])[CH2:19][NH:20][C:21](=[O:27])[O:22][C:23]([CH3:26])([CH3:25])[CH3:24])([CH3:14])([CH3:13])[CH3:12].C(N(CC)CC)C>C(Cl)Cl>[Si:15]([O:16][CH2:17][C:18](=[O:28])[CH2:19][NH:20][C:21](=[O:27])[O:22][C:23]([CH3:26])([CH3:25])[CH3:24])([C:11]([CH3:14])([CH3:13])[CH3:12])([CH3:30])[CH3:29]

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 10881307Tert-butyl 3-(tert-butyldimethylsilyloxy)-2-hydroxypropylcarbamate

Product 1

HCID 11709260tert-Butyl (3-((tert-butyldimethylsilyl)oxy)-2-oxopropyl)carbamateYield 92%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a stirring solution of oxalyl chloride (13.6 mL, 0.16 mol) in dry CH2Cl2 (150 mL) at −78° C. under N2 was added DMSO (15.2 mL, 0.21 mol) dropwise over 30 min. After complete addition the resulting solution was stirred at −78° C. for 1 h. A solution of tert-butyl 3-(tert-butyldimethyl-silyloxy)-2-hydroxypropylcarbamate (32.6 g, 0.11 mol) in CH2Cl2 (50 mL) was then added dropwise over 20 min. Stirring was continued for a further 1 hour at which time triethylamine (59.6 mL, 0.43 mol) was added. The cooling bath was removed and the reaction mixture was allowed to warm to room temperature. The reaction mixture was partitioned between water (100 mL) and CH2Cl2 (70 mL) and the aqueous layer was extracted with further CH2Cl2 (2×70 mL); the combined organics were dried over Na2SO4 and concentrated under a stream of nitrogen gas. The crude residue was purified over silica gel eluting with 5% ethylacetate in n-hexane to give tert-butyl 3-(tert-butyldimethylsilyloxy)-2-oxopropylcarbamate (29.8 g, 92%) as a pale yellow oil. 1H-NMR (300 MHz; CDCl3) δ ppm: 0.11 (6H, s), 0.94 (9H, s), 1.47 (9H, s), 3.92 (2H, s), 4.26 (2H, d, J 4.6 Hz), 5.22 (1H, br s).

Workup

  1. additionAfter complete addition the resulting solution
  2. stirringStirring
  3. additionwas added
  4. customThe cooling bath was removed
  5. temperatureto warm to room temperature
  6. customThe reaction mixture was partitioned between water (100 mL) and CH2Cl2 (70 mL)
  7. extractionthe aqueous layer was extracted with further CH2Cl2 (2×70 mL)
  8. dry with materialthe combined organics were dried over Na2SO4
  9. concentrationconcentrated under a stream of nitrogen gas
  10. customThe crude residue was purified over silica gel eluting with 5% ethylacetate in n-hexane

Sources & evidence

ORD record
ord-5bae7862b75b4b36aa1f6479103154c6
Source dataset
uspto-grants-2016_04
Patent number
US09302986B2

Reaction notes

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