Cerium(III) chloride → tert-Butyl (3S,6S)-6-{[(tert-butyldimethylsilyl)oxy]methyl}-3-hydroxy-4-methyl-1,2,3,6-tetrahydropyridine-1-carboxylate

HRID 627074Notes

Reaction equation

HRID 627074 reaction equation
[Cl-].[Ce+3].[Cl-].[Cl-].[Si:5]([O:12][CH2:13][C@@H:14]1[CH:19]=[C:18]([CH3:20])[C:17](=[O:21])[CH2:16][N:15]1[C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])([C:8]([CH3:11])([CH3:10])[CH3:9])([CH3:7])[CH3:6].[BH4-].[Na+]>CO.[Cl-].[NH4+].O>[Si:5]([O:12][CH2:13][C@@H:14]1[CH:19]=[C:18]([CH3:20])[C@H:17]([OH:21])[CH2:16][N:15]1[C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])([C:8]([CH3:11])([CH3:9])[CH3:10])([CH3:7])[CH3:6]

Participants

7

Reactant 3

HCID 24636Cerium(III) chlorideHCID 4311764Sodium borohydrideHCID 89852373tert-Butyl (6S)-6-{[(tert-butyldimethylsilyl)oxy]methyl}-4-methyl-3-oxo-1,2,3,6-tetrahydropyridine-1-carboxylate2×

Product 1

HCID 89852486tert-Butyl (3S,6S)-6-{[(tert-butyldimethylsilyl)oxy]methyl}-3-hydroxy-4-methyl-1,2,3,6-tetrahydropyridine-1-carboxylateYield 91.3%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 25517Ammonium ChlorideSolvent

Procedure

To a solution of cerium(III) chloride (14.68 g, 59.57 mmol) and (S)-tert-butyl 2-((tert-butyldimethylsilyloxy)methyl)-4-methyl-5-oxo-5,6-dihydropyridine-1(2H)-carboxylate (Intermediate 7, 21.18 g, 59.57 mmol) in methanol (300 mL) at 0° C. was added sodium borohydride (2.254 g, 59.57 mmol) portionwise. After 15 minutes, the reaction mixture was diluted with saturated ammonium chloride (100 mL) and water (100 mL), then extracted twice with diethyl ether. The organic extracts were washed with brine, dried over magnesium sulfate, filtered and concentrated. Silica gel chromatography (0%-20% ethyl acetate/hexanes) afforded the desired product (19.45 g, 91%) as a colorless oil.

Workup

  1. extractionextracted twice with diethyl ether
  2. washThe organic extracts were washed with brine
  3. dry with materialdried over magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-f158ee2ca3cf4e13a2d995ca44fa243a
Source dataset
uspto-grants-2016_04
Patent number
US09309245B2

Reaction notes

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