Triacetoxyperiodinane → (3S*,4R*)-3-formyl-4-({isopropyl-[4-methoxy-3-(3-methoxy-propoxy)-benzoyl]-amino}-methyl)-pyrrolidine-1-carboxylic acid tert-butyl ester

HRID 1158337

Reaction equation

HRID 1158337 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:12][C@@H:11]([CH2:13][N:14]([CH:31]([CH3:33])[CH3:32])[C:15](=[O:30])[C:16]2[CH:21]=[CH:20][C:19]([O:22][CH3:23])=[C:18]([O:24][CH2:25][CH2:26][CH2:27][O:28][CH3:29])[CH:17]=2)[C@H:10]([CH2:34][OH:35])[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.CCOCC>[C:1]([O:5][C:6]([N:8]1[CH2:12][C@@H:11]([CH2:13][N:14]([CH:31]([CH3:32])[CH3:33])[C:15](=[O:30])[C:16]2[CH:21]=[CH:20][C:19]([O:22][CH3:23])=[C:18]([O:24][CH2:25][CH2:26][CH2:27][O:28][CH3:29])[CH:17]=2)[C@H:10]([CH:34]=[O:35])[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 2

HCID 159087TriacetoxyperiodinaneHCID 59512299(3S,4R)-3-Hydroxymethyl-4-({isopropyl-[4-methoxy-3-(3-methoxy-propoxy)-benzoyl]-amino}-methyl)-pyrrolidine-1-carboxylic acid tert-butyl ester

Product 1

HCID 59512275(3S*,4R*)-3-formyl-4-({isopropyl-[4-methoxy-3-(3-methoxy-propoxy)-benzoyl]-amino}-methyl)-pyrrolidine-1-carboxylic acid tert-butyl ester

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent3×

Procedure

To a well-stirred mixture of (3S*,4R*)-3-hydroxymethyl-4-({isopropyl-[4-methoxy-3-(3-methoxy-propoxy)-benzoyl]-amino}-methyl)-pyrrolidine-1-carboxylic acid tert-butyl ester (600 mg, 1.21 mmol) and Dess-Martin periodinane (272 mg, 1.21 mmol) in CH2Cl2 (10 mL), slowly wet CH2Cl2 (24 μL of water in 2 mL of CH2Cl2) is added. The clear solution becomes cloudy towards the end of wet CH2Cl2 addition. The mixture is diluted with Et2O and concentrated to a few mL of solvent by rotary evaporation. The residue is taken up in Et2O, and washed with a 1:1 10% Na2S2O3/saturated aqueous solution of 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 over Na2SO4, filtered and concentrated under reduced pressure. The crude material is used without further purification in the next step. TLC, Rf (CH2Cl2/MeOH 95:5)=0.3. tR (HPLC, Nucleosil C18 column, 10-100% CH3CN/H2O/5 min, 100% CH3CN/3 min, CH3CN and H2O containing 0.1% TFA, flow: 1.5 ml/min): 5.16 min.

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 solution of 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 over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customThe crude material is used without further purification in the next step
  10. customtR (HPLC, Nucleosil C18 column, 10-100% CH3CN/H2O/5 min, 100% CH3CN/3 min, CH3CN and H2O containing 0.1% TFA, flow: 1.5 ml/min)
  11. custom5.16 min.

Sources & evidence

ORD record
ord-2ffd5e2276b146acb956c884f5a8c730
Source dataset
uspto-grants-2010_10
Patent number
US07807709B2

Linked notes

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