Triacetoxyperiodinane → (3S*,4S*)-3-(tert-Butyl-dimethyl-silanyloxymethyl)-4-formyl-pyrrolidine-1-carboxylic acid tert-butyl ester

HRID 1158346Notes

Reaction equation

HRID 1158346 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:12][C@@H:11]([CH2:13][OH:14])[C@H:10]([C:15]([CH3:23])([CH3:22])[O:16][SiH2:17][C:18]([CH3:21])([CH3:20])[CH3:19])[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O>C(Cl)Cl>[C:1]([O:5][C:6]([N:8]1[CH2:12][C@@H:11]([CH:13]=[O:14])[C@H:10]([C:15]([CH3:23])([CH3:22])[O:16][SiH2:17][C:18]([CH3:21])([CH3:20])[CH3:19])[CH2:9]1)=[O:7])([CH3:3])([CH3:4])[CH3:2]

Participants

4

Reactant 2

HCID 159087TriacetoxyperiodinaneHCID 131728360(3S*,4S*)-3-(tert-butyl-dimethyl-silanyloxymethyl)-4-hydroxymethyl-pyrrolidine-1-carboxylic acid tert-butyl ester

Product 1

HCID 131728359(3S*,4S*)-3-(tert-Butyl-dimethyl-silanyloxymethyl)-4-formyl-pyrrolidine-1-carboxylic acid tert-butyl ester

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Procedure

To a well stirred mixture of (3S,4S)-3-(tert-butyl-dimethyl-silanyloxymethyl)-4-hydroxymethyl-pyrrolidine-1-carboxylic acid tert-butyl ester (8.2 g, 23.73 mmol) and Dess-Martin periodinane (10.06 g, 23.73 mmol) in CH2Cl2 (60 mL), slowly wet CH2Cl2 (0.47 mL of water in 60 mL of CH2Cl2) is added. The clear solution becomes cloudy toward the end of wet CH2Cl2 addition and is further stirred over-night. Then concentrated to a few mL of solvent by rotary evaporation and taken up in Et2O. A solution of 1:1 10% Na2S2O3/saturated aqueous NaHCO3 is added. The layers are separated and the organic extract is washed successively with H2O and brine. The aqueous washings are back-extracted with Et2O, and this organic layer is washed with H2O and brine. The combined organic layers are dried with Na2SO4, filtered and concentrated. The crude mixture is used in the next step without further purification. TLC, Rf (CH2Cl2/MeOH 95:5)=0.42. MS (LC-MS): 244.2 [M+H-Boc]+; tR (HPLC, C18 column, 5-100% CH3CN/H2O/6 min, 100% CH3CN/2 min, CH3CN and H2O containing 0.1% TFA, flow: 1 mL/min): 6.45 min.

Workup

  1. additionis added
  2. waitis further stirred over-night
  3. concentrationThen concentrated to a few mL of solvent by rotary evaporation
  4. additionA solution of 1:1 10% Na2S2O3/saturated aqueous NaHCO3 is added
  5. customThe layers are separated
  6. extractionthe organic extract
  7. washis washed successively with H2O and brine
  8. extractionThe aqueous washings are back-extracted with Et2O
  9. washthis organic layer is washed with H2O and brine
  10. dry with materialThe combined organic layers are dried with Na2SO4
  11. filtrationfiltered
  12. concentrationconcentrated
  13. customThe crude mixture is used in the next step without further purification
  14. customtR (HPLC, C18 column, 5-100% CH3CN/H2O/6 min, 100% CH3CN/2 min, CH3CN and H2O containing 0.1% TFA, flow: 1 mL/min)
  15. custom6.45 min.

Sources & evidence

ORD record
ord-2fffb0f9714146b5b31ef34613de2aa9
Source dataset
uspto-grants-2010_10
Patent number
US07807709B2

Reaction notes

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