Triacetoxyperiodinane → (3S*,4S*)-4-Formyl-pyrrolidine-1,3-dicarboxylic acid 1-tert-butyl ester 3-ethyl ester

HRID 1158325Notes

Reaction equation

HRID 1158325 reaction equation
[CH2:1]([O:3][C:4]([C@H:6]1[C@H:10]([CH2:11][OH:12])[CH2:9][N:8]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:7]1)=[O:5])[CH3:2].CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O>C(Cl)Cl.CCOCC>[CH2:1]([O:3][C:4]([C@H:6]1[C@H:10]([CH:11]=[O:12])[CH2:9][N:8]([C:13]([O:15][C:16]([CH3:17])([CH3:19])[CH3:18])=[O:14])[CH2:7]1)=[O:5])[CH3:2]

Participants

5

Reactant 2

HCID 159087TriacetoxyperiodinaneHCID 59512291(3S*,4S*)-4-hydroxymethyl-pyrrolidine-1,3-dicarboxylic acid 1-tert-butylester 3-ethyl ester

Product 1

HCID 86622385(3S*,4S*)-4-Formyl-pyrrolidine-1,3-dicarboxylic acid 1-tert-butyl ester 3-ethyl ester

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent3×

Procedure

To a well stirred mixture of (3S*,4S*)-4-hydroxymethyl-pyrrolidine-1,3-dicarboxylic acid 1-tert-butylester 3-ethyl ester (3.21 g, 11.74 mmol) and Dess-Martin periodinane (2.63 g, 11.74 mmol) in CH2Cl2 (30 mL), slowly wet CH2Cl2 (232 μL of water in 10 mL of CH2Cl2) is added. The clear solution becomes cloudy toward the end of wet CH2Cl2 addition. The mixture is diluted with Et2O, then concentrated to a few mL of solvent by rotary evaporation. The residue is taken up in Et2O and then washed with a 1:1 10% Na2S2O3 saturated aqueous NaHCO3, followed by 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 (c-hexane/AcOEt 8:2)=0.2.

Workup

  1. additionis added
  2. concentrationconcentrated to a few mL of solvent by rotary evaporation
  3. washwashed with a 1:1 10% Na2S2O3 saturated aqueous NaHCO3
  4. extractionThe aqueous washings are back-extracted with Et2O
  5. washthis organic layer is washed with H2O and brine
  6. dry with materialThe combined organic layers are dried with Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe crude mixture is used in the next step without further purification

Sources & evidence

ORD record
ord-ca89a394ac5a4c7bacb98891297105b9
Source dataset
uspto-grants-2010_10
Patent number
US07807709B2

Reaction notes

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