3-Boc-2,2-dimethyloxazolidine-4-carboxaldehyde, (S)-(-)- → 117487-58-8

HRID 2200834Notes

Reaction equation

HRID 2200834 reaction equation
[C:1]([O:5][C:6]([N:8]1[C@H:12]([CH:13]=[O:14])[CH2:11][O:10][C:9]1([CH3:16])[CH3:15])=[O:7])([CH3:4])([CH3:3])[CH3:2].[CH:17]([Mg]Br)=[CH2:18]>C1COCC1>[C:1]([O:5][C:6]([N:8]1[C@H:12]([C@H:13]([OH:14])[CH:17]=[CH2:18])[CH2:11][O:10][C:9]1([CH3:16])[CH3:15])=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

4

Reactant 2

HCID 1798243-Boc-2,2-dimethyloxazolidine-4-carboxaldehyde, (S)-(-)-HCID 178418507HCID 178418507, compound

Product 1

HCID 10777541117487-58-8Yield 62%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a −78° C. solution of (S)-Garner aldehyde (3, 7.0 g, 30.5 mmol) in dry THF (50 mL) under N2 was slowly added vinylmagnesium bromide (92 mL, 92 mmol, a 1 M solution in THF) via cannula. After the cloudy yellow solution was stirred for 2 h at −78° C., it was warmed to 0° C., and the reaction was quenched with saturated aqueous NH4Cl solution (60 mL). The product was extracted with Et2O (2×60 mL). The combined organic layers were washed with brine (60 mL), dried (Na2SO4), and concentrated. The mixture of erythro and threo diastereomers was separated by column chromatography by gravity (hexane/EtOAc 5:1) to afford 4 (4.8 g, 62%) and its C3-epimer 4a (0.8 g, 10.2%). Compound 4: [α]25D −37.7° (c 1.8, CHCl3); Rf 0.26 (EtOAc/hexane 1:3); 1H NMR (CDCl3) δ 1.48 (s, 3H), 1.50 (s, 9H), 1.58 (s, 3H), 3.91 (m, 2H), 3.98 (m, 1H), 4.25 (m, 1H), 4.39 (m, 1H), 5.24 (m, 1H), 5.38 (m, 1H), 5.85 (m, 1H); 13C NMR (CDCl3) δ 24.2, 26.3, 28.3, 61.8, 64.4, 73.3, 81.4, 94.4, 116.1, 117.8, 137.6, 155.0; ESI-HRMS [M+Na]+ C13H23NO4Na calcd for m/z 280.1525, found 280.1519.

Workup

  1. customTo a −78° C.
  2. temperatureit was warmed to 0° C.
  3. customthe reaction was quenched with saturated aqueous NH4Cl solution (60 mL)
  4. extractionThe product was extracted with Et2O (2×60 mL)
  5. washThe combined organic layers were washed with brine (60 mL)
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated
  8. additionThe mixture of erythro and threo diastereomers
  9. customwas separated by column chromatography by gravity (hexane/EtOAc 5:1)

Sources & evidence

ORD record
ord-049369a942de431fabd6a234eb0a5b15
Source dataset
uspto-grants-2016_06
Patent number
US09359389B2

Reaction notes

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