m-Chloroperbenzoic acid → Benzyl 2-(di-tert-butoxyphosphoryloxy)ethyl(ethyl)carbamate

HRID 1476285Notes

Reaction equation

HRID 1476285 reaction equation
[CH2:1]([N:3]([CH2:14][CH2:15][OH:16])[C:4](=[O:13])[O:5][CH2:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)[CH3:2].C(N(CC)[P:20]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])[O:21][C:22]([CH3:25])([CH3:24])[CH3:23])C.N1C=NN=N1.C1C=C(Cl)C=C(C(OO)=[O:46])C=1.S(=O)(O)[O-].[Na+]>C1COCC1>[C:27]([O:26][P:20]([O:16][CH2:15][CH2:14][N:3]([CH2:1][CH3:2])[C:4](=[O:13])[O:5][CH2:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)([O:21][C:22]([CH3:23])([CH3:24])[CH3:25])=[O:46])([CH3:28])([CH3:29])[CH3:30]

Participants

7

Reactant 5

HCID 70297m-Chloroperbenzoic acidHCID 4251849Di-tert-butyl diethylphosphoramiditeHCID 14266447Benzyl ethyl(2-hydroxyethyl)carbamate2×HCID 23665763Sodium BisulfiteHCID 178418441HCID 178418441, compound

Product 1

HCID 58080156Benzyl 2-(di-tert-butoxyphosphoryloxy)ethyl(ethyl)carbamateYield 60%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of benzyl ethyl(2-hydroxyethyl)carbamate (INTERMEDIATE 47, 1.0 g, 4.48 mmol) and di-tert-butyl diethylphosphoramidite (4.47 ml, 16.1 mmol) in THF (146 ml) was treated with tetrazole (1.57 g, 22.39 mmol) in one portion. The resulting mixture was stirred at r.t for 50 minutes and the clear solution became cloudy. The mixture was cooled using an acetone/dry ice bath (˜−77° C.) and m-CPBA (6.96 g) was added over the course of ˜1 minute. The mixture was stirred under these conditions for 20 minutes and subsequently allowed to warm to r.t. over 10 minutes. Sodium bisulfite (aq., 10% w/v, 3.41 ml) was added and the mixture was stirred for 10 minutes, concentrated in vacuo, diluted with EtOAc (200 ml), and washed with sodium bisulfite (aq., 100 ml), and NaHCO3 (aq., 5% w/v, 100 ml). The organic layer was dried (Na2SO4), filtered, and evaporated under reduced pressure. The concentrate was purified by column chromatography (ISCO, silica gel column, eluting with 0→100% EtOAc in hexanes) to give the title compound (1.1 g, yield: 60%).

Workup

  1. temperatureThe mixture was cooled
  2. additionwas added over the course of ˜1 minute
  3. stirringThe mixture was stirred under these conditions for 20 minutes
  4. stirringthe mixture was stirred for 10 minutes
  5. concentrationconcentrated in vacuo
  6. additiondiluted with EtOAc (200 ml)
  7. washwashed with sodium bisulfite (aq., 100 ml), and NaHCO3 (aq., 5% w/v, 100 ml)
  8. dry with materialThe organic layer was dried (Na2SO4)
  9. filtrationfiltered
  10. customevaporated under reduced pressure
  11. customThe concentrate was purified by column chromatography (ISCO, silica gel column, eluting with 0→100% EtOAc in hexanes)

Sources & evidence

ORD record
ord-739221dde924447bb211b4d400343677
Source dataset
uspto-grants-2015_04
Patent number
US09018381B2

Reaction notes

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