Dimethyl Sulfoxide → 5-(Tert-butyldimethylsilyloxy)cyclooctanone

HRID 402543Notes

Reaction equation

HRID 402543 reaction equation
CS(C)=O.C(Cl)(=O)C(Cl)=O.[C:11]([Si:15]([CH3:27])([CH3:26])[O:16][C@@H:17]1[CH2:24][CH2:23][CH2:22][C@H:21]([OH:25])[CH2:20][CH2:19][CH2:18]1)([CH3:14])([CH3:13])[CH3:12].C(N(CC)CC)C.[Cl-].[NH4+]>ClCCl>[C:11]([Si:15]([CH3:27])([CH3:26])[O:16][CH:17]1[CH2:24][CH2:23][CH2:22][C:21](=[O:25])[CH2:20][CH2:19][CH2:18]1)([CH3:14])([CH3:13])[CH3:12]

Participants

7

Reactant 5

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 25517Ammonium ChlorideHCID 65578Oxalyl chlorideHCID 178455305HCID 178455305, compound

Product 1

HCID 109780905-(Tert-butyldimethylsilyloxy)cyclooctanoneYield 101%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent4×

Conditions

Temperature
-78 °C

Procedure

A solution of 4.5 g (58 mmol) of dimethyl sulphoxide in 25 mL dichloromethane was added dropwise to a stirred solution of 3.7 g (29 mmol) of oxalyl chloride in 50 mL of dichloromethane at −78° C. The solution was stirred for 30 minutes at −78° C. and then 5.0 g (19.3 mmol) of cis-5-(tert-butyl-dimethyl-silanyloxy)-cyclooctanol (57) in 30 mL of dichloromethane was added dropwise keeping the temperature at −78° C. After stirring for 30 minutes, 9.8 g (97 mmol) of triethylamine was added dropwise and the temperature allowed to warm to −30° C. Further 50 mL of dichloromethane were added and the solution stirred for 1 h at −30° C. With stirring 300 mL of a saturated ammonium chloride solution were added portionwise and then the organic layer was separated. After washing with further ammonium chloride solution, the organic phase was dried over magnesium sulfate, filtered and evaporated to give 5.0 g of the desired product as a yellow oil which was used without purification. Rt=1.96 min (Method C). Detected mass: 257.3 (M+H+).

Workup

  1. customat −78° C
  2. stirringAfter stirring for 30 minutes
  3. temperatureto warm to −30° C
  4. stirringthe solution stirred for 1 h at −30° C
  5. additionwere added portionwise
  6. customthe organic layer was separated
  7. washAfter washing with further ammonium chloride solution
  8. dry with materialthe organic phase was dried over magnesium sulfate
  9. filtrationfiltered
  10. customevaporated

Sources & evidence

ORD record
ord-80cbb0378d394cb7992a421cad579480
Source dataset
uspto-grants-2014_06
Patent number
US08742116B2

Reaction notes

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