Diisopropylethylamine → tert-butyl (2R,3R,4S)-5-azido-3-(tert-butyldimethylsilyloxy)-1-hydroxy-4-methylpentan-2-ylcarbamate

HRID 924426Notes

Reaction equation

HRID 924426 reaction equation
C1(C)C=CC(S([O-])(=O)=O)=CC=1.[NH+]1C=CC=CC=1.[N:18]([CH2:21][C@H:22]([CH3:46])[C@H:23]([C@H:32]1[CH2:36][O:35]C(C)(C)[N:33]1[C:39]([O:41][C:42]([CH3:45])([CH3:44])[CH3:43])=[O:40])[O:24][Si:25]([C:28]([CH3:31])([CH3:30])[CH3:29])([CH3:27])[CH3:26])=[N+:19]=[N-:20].CCN(C(C)C)C(C)C.CC(OC(OC(OC(C)(C)C)=O)=O)(C)C>CCO>[N:18]([CH2:21][C@H:22]([CH3:46])[C@@H:23]([O:24][Si:25]([C:28]([CH3:31])([CH3:30])[CH3:29])([CH3:26])[CH3:27])[C@H:32]([NH:33][C:39](=[O:40])[O:41][C:42]([CH3:45])([CH3:43])[CH3:44])[CH2:36][OH:35])=[N+:19]=[N-:20]

Participants

6

Reactant 4

HCID 81531DiisopropylethylamineHCID 90495Di-tert-butyl dicarbonateHCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)HCID 59226479(R)-tert-butyl 4-((1R,2S)-3-azido-1-(tert-butyldimethylsilyloxy)-2-methylpropyl)-2,2-dimethyloxazolidine-3-carboxylate

Product 1

HCID 86639730tert-butyl (2R,3R,4S)-5-azido-3-(tert-butyldimethylsilyloxy)-1-hydroxy-4-methylpentan-2-ylcarbamateYield 56%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Pyridinium p-toluenesulfonate (1.3 g, 5.2 mmol) was added to a solution of tert-butyl (4R)-4-((1R,2S)-3-azido-1-{[tert-butyl(dimethyl)silyl]oxy}-2-methylpropyl)-2,2-dimethyl-1,3-oxazolidine-3-carboxylate (1.09 g, 2.6 mmol) in EtOH (15 mL). The mixture was heated under reflux for 2 days. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure. The residue was dissolved in DCM (25 mL), and DIPEA (0.67 mL, 3.8 mmol) was added followed by Boc2O (0.67 g, 3.1 mmol). The mixture was stirred at room temperature for 5 h, and then concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (eluting with 0-25% EtOAc in hexanes) to provide the sub-title compound (0.56 g, 56%). LCMS calc. for C12H29N4O2Si (M+H-Boc)+: m/z=289.2. found 289.2.

Workup

  1. temperatureThe mixture was heated
  2. temperatureunder reflux for 2 days
  3. concentrationthe reaction mixture was concentrated under reduced pressure
  4. dissolutionThe residue was dissolved in DCM (25 mL)
  5. concentrationconcentrated under reduced pressure
  6. customThe residue was purified by flash chromatography on silica gel (eluting with 0-25% EtOAc in hexanes)

Sources & evidence

ORD record
ord-9e42a8e061244ab5904c8de96a74b515
Source dataset
uspto-grants-2016_03
Patent number
US09278950B2

Reaction notes

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