Lithium acetate → (Z)-ethyl 4-(2-chloro-6-(3-ethoxy-1-hydroxy-3-oxoprop-1-enyl)phenyl)-tetrahydro-2H-pyran-4-carboxylate

HRID 2078347Notes

Reaction equation

HRID 2078347 reaction equation
C([O-])(=[O:3])C.[Li+].[Cl:6][C:7]1[CH:12]=[CH:11][CH:10]=[C:9]([C:13]#[C:14][C:15]([O:17][CH2:18][CH3:19])=[O:16])[C:8]=1[C:20]1([C:26]([O:28][CH2:29][CH3:30])=[O:27])[CH2:25][CH2:24][O:23][CH2:22][CH2:21]1>C(O)(C(F)(F)F)=O.CCOC(C)=O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[Cl:6][C:7]1[CH:12]=[CH:11][CH:10]=[C:9](/[C:13](/[OH:3])=[CH:14]/[C:15]([O:17][CH2:18][CH3:19])=[O:16])[C:8]=1[C:20]1([C:26]([O:28][CH2:29][CH3:30])=[O:27])[CH2:25][CH2:24][O:23][CH2:22][CH2:21]1

Participants

6

Reactant 2

HCID 3474584Lithium acetateHCID 67099623HCID 67099623, compound

Product 1

HCID 86629261(Z)-ethyl 4-(2-chloro-6-(3-ethoxy-1-hydroxy-3-oxoprop-1-enyl)phenyl)-tetrahydro-2H-pyran-4-carboxylateYield 31%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 6422Trifluoroacetic acidSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of lithium acetate (0.21 g, 3.2 mmol) in 5 mL TFA at room temperature was treated with ethyl 4-(2-chloro-6-(3-ethoxy-3-oxoprop-1-ynyl)phenyl)-tetrahydro-2H-pyran-4-carboxylate (1.18 g, 3.2 mmol), and palladium(II) acetate (0.036 g, 0.16 mmol). The reaction was stirred at room temperature for 2 hours. The residue was diluted with 100 mL EtOAc, washed with water (3×20 mL), saturated NaCl (20 mL), dried over anhydrous sodium sulfate, and concentrated. The concentrate was purified by column chromatography (10-20% EtOAc/hexane) to give 0.38 g yellow oil. MS m/e: (M+H)+ 383.

Workup

  1. washwashed with water (3×20 mL), saturated NaCl (20 mL)
  2. dry with materialdried over anhydrous sodium sulfate
  3. concentrationconcentrated
  4. customThe concentrate was purified by column chromatography (10-20% EtOAc/hexane)

Sources & evidence

ORD record
ord-910426f337b94a7ab6067b5e848f8a54
Source dataset
uspto-grants-2011_04
Patent number
US07928139B2

Reaction notes

Loading…