Water → HCID 57771620, compound

HRID 2070596Notes

Reaction equation

HRID 2070596 reaction equation
[CH3:1][O:2][C:3]([CH:5]1[CH2:32][CH2:31][CH2:30][C@@:7]2([CH2:11][C@H:10]([O:12][Si:13]([C:26]([CH3:29])([CH3:28])[CH3:27])([C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=3)[C:14]3[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=3)[CH2:9][CH2:8]2)[CH:6]1O)=[O:4].CS(Cl)(=O)=O.O>N1C=CC=CC=1>[CH3:1][O:2][C:3]([C:5]1[CH2:32][CH2:31][CH2:30][C@@:7]2([CH2:11][C@H:10]([O:12][Si:13]([C:26]([CH3:29])([CH3:27])[CH3:28])([C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=3)[C:14]3[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=3)[CH2:9][CH2:8]2)[CH:6]=1)=[O:4]

Participants

5

Reactant 3

HCID 962WaterHCID 31297Methanesulfonyl chlorideHCID 57771543HCID 57771543, compound

Product 1

HCID 57771620HCID 57771620, compoundYield 36.3%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

To a solution of the crude (2R,5R)-2-(tert-butyldiphenylsilanyloxy)-6-hydroxy-spiro[4.5]decane-7-carboxylic acid methyl ester (1.76 g) obtained in Step 5 in pyridine (5 mL) was added methanesulfonyl chloride (0.25 mL) under ice-cooling, followed by stirring the mixture at room temperature for 15 hours. Then, to the reaction mixture was added water, followed by extraction with ethyl acetate. The organic layer was washed with saturated brine, dried and concentrated. The residue was dissolved in tetrahydrofuran (10 mL). To this solution was added 1,8-diazabicyclo[5.4.0]undec-7-ene (0.88 mL), followed by stirring the mixture at 70° C. for 3.5 hours. After cooling down to room temperature and adding water, the reaction mixture was extracted with ethyl acetate. The organic layer was washed successively with 1N aqueous hydrochloric acid solution and saturated brine, dried and concentrated. The residue was purified by column chromatography on silica gel (ethyl acetate:hexane (volume ratio)=1:30 to 1:25) to give (2R,5R)-2-(tert-butyldiphenylsilanyloxy)-spiro[4.5]dec-6-en e-7-carboxylic acid methyl ester (0.615 g).

Workup

  1. temperaturecooling
  2. extractionfollowed by extraction with ethyl acetate
  3. washThe organic layer was washed with saturated brine
  4. customdried
  5. concentrationconcentrated
  6. dissolutionThe residue was dissolved in tetrahydrofuran (10 mL)
  7. additionTo this solution was added 1,8-diazabicyclo[5.4.0]undec-7-ene (0.88 mL)
  8. stirringby stirring the mixture at 70° C. for 3.5 hours
  9. temperatureAfter cooling down to room temperature
  10. additionadding water
  11. extractionthe reaction mixture was extracted with ethyl acetate
  12. washThe organic layer was washed successively with 1N aqueous hydrochloric acid solution and saturated brine
  13. customdried
  14. concentrationconcentrated
  15. customThe residue was purified by column chromatography on silica gel (ethyl acetate:hexane (volume ratio)=1:30 to 1:25)

Sources & evidence

ORD record
ord-fe63fe1d80944b4b8ec8241431deab9b
Source dataset
uspto-grants-2012_10
Patent number
US08299296B2

Reaction notes

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