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

HRID 384062Notes

Reaction equation

HRID 384062 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-bf62d6c7c30f48cfb84a527de268c497
Source dataset
uspto-grants-2013_02
Patent number
US08367697B2

Reaction notes

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