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

HRID 1499471Notes

Reaction equation

HRID 1499471 reaction equation
[N:1]([CH2:4][C@H:5]([CH3:29])[C@H:6]([C@H:15]1[CH2:19][O:18]C(C)(C)[N:16]1[C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[O:7][Si:8]([C:11]([CH3:14])([CH3:13])[CH3:12])([CH3:10])[CH3:9])=[N+:2]=[N-:3].C1(C)C=CC(S([O-])(=O)=O)=CC=1.[NH+]1C=CC=CC=1.CCN(C(C)C)C(C)C.C(OC(OC(C)(C)C)=O)(OC(C)(C)C)=O>CCO>[N:1]([CH2:4][C@H:5]([CH3:29])[C@@H:6]([O:7][Si:8]([C:11]([CH3:14])([CH3:13])[CH3:12])([CH3:9])[CH3:10])[C@H:15]([NH:16][C:22](=[O:23])[O:24][C:25]([CH3:28])([CH3:26])[CH3:27])[CH2:19][OH:18])=[N+:2]=[N-:3]

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

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), pyridinium p-toluenesulfonate (1.3 g, 5.2 mmol) was added. 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 di-tert-butyl dicarbonate (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 chromatography on silica gel (0-25% EtOAc in hexanes) to afford 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 chromatography on silica gel (0-25% EtOAc in hexanes)

Sources & evidence

ORD record
ord-5b7e6c6c49da44bfa2ad488d277014fb
Source dataset
uspto-grants-2015_12
Patent number
US09200004B2

Reaction notes

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