Chloride → (2S,5S)-tert-butyl 2-((tert-butyldimethylsilyloxy)methyl)-5-hydroxy-5,6-dihydropyridine-1(2H)-carboxylate

HRID 627155Notes

Reaction equation

HRID 627155 reaction equation
[Cl-].[Si:2]([O:9][CH2:10][C@@H:11]1[CH:16]=[CH:15][C:14](=[O:17])[CH2:13][N:12]1[C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])([C:5]([CH3:8])([CH3:7])[CH3:6])([CH3:4])[CH3:3].[BH4-].[Na+]>CO>[Si:2]([O:9][CH2:10][C@@H:11]1[CH:16]=[CH:15][C@H:14]([OH:17])[CH2:13][N:12]1[C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])([C:5]([CH3:8])([CH3:7])[CH3:6])([CH3:4])[CH3:3]

Participants

5

Reactant 3

HCID 312ChlorideHCID 4311764Sodium borohydrideHCID 89852524(S)-Tert-butyl 2-(((tert-butyldimethylsilyl)oxy)methyl)-5-oxo-5,6-dihydropyridine-1(2H)-carboxylate2×

Product 1

HCID 89852438(2S,5S)-tert-butyl 2-((tert-butyldimethylsilyloxy)methyl)-5-hydroxy-5,6-dihydropyridine-1(2H)-carboxylateYield 64.6%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a stirred solution of cerious chloride (4.36 g, 11.71 mmol) and (S)-tert-butyl 2-((tert-butyldimethylsilyloxy)methyl)-5-oxo-5,6-dihydropyridine-1(2H)-carboxylate (Intermediate 50, 4.00 g, 11.71 mmol) in 50 mL MeOH at 0° C., NaBH4 (0.443 g, 11.71 mmol) was added as a solid. The mixture was stirred at ambient temp for 15 minutes. The mixture was concentrated and diluted with 10% citric acid (aq), H2O and ethyl acetate. The organic layer was separated and washed with brine, dried over MgSO4, filtered and concentrated to give a residue which was purified by silica gel column (25 g, 20-40% Hex/EA) to give the desired product (2.6 g) as a colorless oil.

Workup

  1. concentrationThe mixture was concentrated
  2. additiondiluted with 10% citric acid (aq), H2O and ethyl acetate
  3. customThe organic layer was separated
  4. washwashed with brine
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customto give a residue which
  9. customwas purified by silica gel column (25 g, 20-40% Hex/EA)

Sources & evidence

ORD record
ord-63f39477994b44c9af72b7f4c4722685
Source dataset
uspto-grants-2016_04
Patent number
US09309245B2

Reaction notes

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