Potassium Hydroxide → Tert-butyl 3-(3-bromophenyl)-3-(2-ethoxy-2-oxoethyl)azetidine-1-carboxylate

HRID 1920850Notes

Reaction equation

HRID 1920850 reaction equation
[OH-].[K+].[Br:3][C:4]1[CH:5]=[C:6](B(O)O)[CH:7]=[CH:8][CH:9]=1.[CH2:13]([O:15][C:16](=[O:29])[CH:17]=[C:18]1[CH2:21][N:20]([C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[CH2:19]1)[CH3:14]>O1CCOCC1.[Cl-].[Na+].O>[Br:3][C:4]1[CH:5]=[C:6]([C:18]2([CH2:17][C:16]([O:15][CH2:13][CH3:14])=[O:29])[CH2:19][N:20]([C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[CH2:21]2)[CH:7]=[CH:8][CH:9]=1

Participants

6

Reactant 3

HCID 14797Potassium HydroxideHCID 2734318(3-Bromophenyl)boronic acidHCID 44195530tert-Butyl 3-(2-ethoxy-2-oxoethylidene)azetidine-1-carboxylate

Product 1

HCID 57969607Tert-butyl 3-(3-bromophenyl)-3-(2-ethoxy-2-oxoethyl)azetidine-1-carboxylateYield 79%

Reagents, catalysts & solvents 2

HCID 312751,4-DioxaneSolvent2×HCID 57417360Sodium chloride; waterSolvent

Procedure

To a solution of [RhCl(COD)]2 (63 mg, 0.031 mmol) in dioxane (10 mL) was added aqueous KOH (1.5M, 8.29 mmol, 5.53 mL), followed by (3-bromophenyl)boronic acid (1.67 g, 8.29 mmol). Then a solution of the tert-butyl 3-(2-ethoxy-2-oxoethylidene)azetidine-1-carboxylate in dioxane (7.5 mL) was added. The reaction mixture was microwaved at 100° C. for 5 min at 300 W. Brine was added and the mixture was extracted twice with ethyl acetate. The combined organics were washed with brine and then dried (MgSO4), filtered and concentrated. Purification by column chromatography (4/1 Pet ether/ethyl acetate) gave the Michael adduct (1.31 g, 79%) as a light yellow oil.

Workup

  1. customThe reaction mixture was microwaved at 100° C. for 5 min at 300 W
  2. extractionthe mixture was extracted twice with ethyl acetate
  3. washThe combined organics were washed with brine
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customPurification by column chromatography (4/1 Pet ether/ethyl acetate)

Sources & evidence

ORD record
ord-80227f3fc3b34360ac6f972c2062adf3
Source dataset
uspto-grants-2012_05
Patent number
US08173635B2

Reaction notes

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