Stannous Chloride → 3-(2-Chloro-4-methoxycarbonylmethyl-phenyl)-3-oxo-propionic acid tert-butyl ester

HRID 1162529

Reaction equation

HRID 1162529 reaction equation
[C:1]([O:5][C:6](=[O:10])[CH:7]=[N+]=[N-])([CH3:4])([CH3:3])[CH3:2].[Sn](Cl)Cl.[CH3:14][O:15][C:16](=[O:27])[CH2:17][C:18]1[CH:23]=[CH:22][C:21]([CH:24]=[O:25])=[C:20]([Cl:26])[CH:19]=1>C(Cl)Cl.[Cl-].[Na+].O>[C:1]([O:5][C:6](=[O:10])[CH2:7][C:24]([C:21]1[CH:22]=[CH:23][C:18]([CH2:17][C:16]([O:15][CH3:14])=[O:27])=[CH:19][C:20]=1[Cl:26])=[O:25])([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 3

HCID 24479Stannous ChlorideHCID 5097903Tert-butyl 2-diazoacetateHCID 59520437Methyl (3-chloro-4-formylphenyl)acetate

Product 1

HCID 686481833-(2-Chloro-4-methoxycarbonylmethyl-phenyl)-3-oxo-propionic acid tert-butyl ester

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 57417360Sodium chloride; waterSolvent

Procedure

A flame-dried flask is charged with tert-butyl-diazoacetate (0.62 mL, 4.48 mmol) and anhydrous tin(II) chloride (168 mg, 0.88 mmol) in dry DCM (10 mL). (3-Chloro-4-formyl-phenyl)-acetic acid methyl ester 14 (500 mg, 2.35 mmol) is dissolved in DCM (5 mL) and added dropwise to the reaction mixture. After stirring for 6 h at room temperature the reaction mixture is poured into brine (50 mL) and extracted with ether (3×50 mL). The combined organic layers are dried (MgSO4), filtered, concentrated and purified on reverse phase HPLC (H2O/MeCN gradient) to afford 3-(2-Chloro-4-methoxycarbonylmethyl-phenyl)-3-oxo-propionic acid tert-butyl ester 56 as a white solid: MS calculated for C16H19Cl2NaO5 (M+Na+) 349.1, found 349.1.

Workup

  1. additionadded dropwise to the reaction mixture
  2. extractionextracted with ether (3×50 mL)
  3. dry with materialThe combined organic layers are dried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated
  6. custompurified on reverse phase HPLC (H2O/MeCN gradient)

Sources & evidence

ORD record
ord-f918d03da3d3488db19f7cfa0a76c7c2
Source dataset
uspto-grants-2010_10
Patent number
US07820705B2

Linked notes

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