Ethyl Acetate → 1,1-Dimethylethyl 3-hydroxy-3-(2-hydroxy-1,1-dimethylethyl)-1-azetidinecarboxylate

HRID 474007Notes

Reaction equation

HRID 474007 reaction equation
C([O:3][C:4]([C:6]([C:9]1([OH:20])[CH2:12][N:11]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:10]1)([CH3:8])[CH3:7])=O)C.CC(C[AlH]CC(C)C)C.[NH4+].[Cl-].C(OCC)(=O)C>C(Cl)Cl>[OH:20][C:9]1([C:6]([CH3:8])([CH3:7])[CH2:4][OH:3])[CH2:12][N:11]([C:13]([O:15][C:16]([CH3:17])([CH3:18])[CH3:19])=[O:14])[CH2:10]1

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 14487Diisobutylaluminum hydrideHCID 25517Ammonium ChlorideHCID 59420819Ethyl 1-[(1,1-dimethylethoxy)carbonyl]-3-hydroxy-α,α-dimethyl-3-azetidineacetate

Product 1

HCID 594207111,1-Dimethylethyl 3-hydroxy-3-(2-hydroxy-1,1-dimethylethyl)-1-azetidinecarboxylateYield 47%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

A solution of tert-butyl 3-(2-(ethoxycarbonyl)propan-2-yl)-3-hydroxyazetidine-1-carboxylate (0.50 g, 1.74 mmol) in DCM (5 ml) was cooled to −78° C. A solution of DIBAL-H in DCM (5.23 mmol, 5.23 ml, 1M) was added dropwise and the solution allowed to warm to 0° C. and stirred for 4 hrs. Sat NH4Cl (20 ml) and ethyl acetate (40 ml) was added. The organic layer washed with brine (30 ml), dried (Na2SO4), and concentrated to give an oil. The oil was purified by flash column chromatography eluting with 30 to 70% ethylacetate/hexanes to give the title compound as a colorless oil 0.20 g, 47%. 1H NMR (CDCl3, 400 Mhz) 1.01 (6H, s), 1.43 (9H, s), 3.58 (2H, s), 3.75 (2H, d), 4.03 (2H, d).

Workup

  1. washThe organic layer washed with brine (30 ml)
  2. dry with materialdried (Na2SO4)
  3. concentrationconcentrated
  4. customto give an oil
  5. customThe oil was purified by flash column chromatography
  6. washeluting with 30 to 70% ethylacetate/hexanes

Sources & evidence

ORD record
ord-a724f50ee38448988e2686eb23d86244
Source dataset
uspto-grants-2014_01
Patent number
US08637511B2

Reaction notes

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