Water → 3-(2-Methylsulfanyl-pyrimidin-4-yl)-3-oxo-propionic acid tert-butyl ester

HRID 1455256Notes

Reaction equation

HRID 1455256 reaction equation
[C:1]([O:5][C:6](=[O:18])[CH2:7][CH:8]([OH:17])[C:9]1[CH:14]=[CH:13][N:12]=[C:11]([S:15][CH3:16])[N:10]=1)([CH3:4])([CH3:3])[CH3:2].CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.O.[O-]S(S([O-])=O)=O.[Na+].[Na+]>C(Cl)Cl>[C:1]([O:5][C:6](=[O:18])[CH2:7][C:8]([C:9]1[CH:14]=[CH:13][N:12]=[C:11]([S:15][CH3:16])[N:10]=1)=[O:17])([CH3:3])([CH3:4])[CH3:2]

Participants

6

Reactant 4

HCID 962WaterHCID 24489Sodium DithioniteHCID 159087TriacetoxyperiodinaneHCID 574380943-Hydroxy-3-(2-methylsulfanyl-pyrimidin-4-yl)-propionic acid tert-butyl ester

Product 1

HCID 574380693-(2-Methylsulfanyl-pyrimidin-4-yl)-3-oxo-propionic acid tert-butyl esterYield 95%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of 3-hydroxy-3-(2-methylsulfanyl-pyrimidin-4-yl)-propionic acid tert-butyl ester, 18, (5.6 g, 20.9 mmol) in CH2Cl2 is added Dess-Martin periodinane (10.7 g, 25.1 mmol) followed by H2O (0.5 mL, 25.1 mmol). After stirring 1 h at room temperature, the solution is poured into aqueous saturated Na2S2O4. The aqueous phase is extracted with CH2Cl2, then EtOAc. The combined organic phases are dried (MgSO4), filtered and concentrated in vacuo. The crude residue is purified over silica (10% EtOAc/hexanes) to afford 5.6 g (95% yield) of the desired product. 1H NMR (300 MHz, CDCl3) (observed 3:1 mixture of enol:keto tautomers) enol tautomer: δ 12.34 (s, OH), 8.67 (d, J=5.1 Hz, 1H), 7.48 (d, J=5.1 Hz, 1H), 6.35 (s, 1H), 2.62 (s, 3H), 1.57 (s, 9H); ESI+ MS: m/z (rel intensity) 269.1 (30, M++H).

Workup

  1. extractionThe aqueous phase is extracted with CH2Cl2
  2. dry with materialThe combined organic phases are dried (MgSO4)
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. customThe crude residue is purified over silica (10% EtOAc/hexanes)

Sources & evidence

ORD record
ord-b27ff14e886340019bf17652d54723d5
Source dataset
uspto-grants-2009_01
Patent number
US07482356B2

Reaction notes

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