Benzyl Alcohol → HCID 86696714, compound

HRID 2365859Notes

Reaction equation

HRID 2365859 reaction equation
C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:8])C=CC=CC=1.C([N:20]([CH2:23][CH3:24])[CH2:21]C)C.[O:25]=[C:26]1C2[CH2:32][CH:28]([CH2:29]C2C(O)=O)[O:27]1.[C:36]1([CH2:42][OH:43])[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1>C1(C)C=CC=CC=1>[O:25]=[C:26]1[CH:24]2[CH2:32][CH:28]([CH2:29][CH:23]2[NH:20][C:21](=[O:8])[O:43][CH2:42][C:36]2[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=2)[O:27]1

Participants

6

Reactant 4

HCID 244Benzyl AlcoholHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 462449653-Oxo-2-oxabicyclo[2.2.1]heptane-5-carboxylic acid

Product 1

HCID 86696714HCID 86696714, compoundYield 72%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

Diphenylphosphoryl azide (“DPPA”) (0.97 g, 3.5 mmol) and triethylamine (384 mg, 3.80 mmol) were added to a solution of 3-oxo-2-oxa-bicyclo[2.2.1]heptane-5-carboxylic acid (0.50 g, 3.2 mmol; prepared according to WO 2008/092955) in dry toluene (5.0 mL). The resulting mixture was stirred at 100° C. under nitrogen atmosphere. After adding phenylmethanol (354 mg, 3.50 mmol), the mixture was stirred at 130° C. for another 2 hours. After being quenched with water (1 mL), the mixture was diluted with ethyl acetate (300 mL), washed with saturated brine (3×50 mL), dried over anhydrous sodium sulfate, and then concentrated. The residue was purified by silica gel chromatography eluting with petroleum ether/ethyl acetate (4:1) to give benzyl 3-oxo-2-oxa-bicyclo[2.2.1]heptan-5-ylcarbamate (600 mg, 72% yield) as a solid. 1H NMR (500 MHz, CDCl3) δ 7.80-7.74 (m, 1H), 7.39-7.31 (m, 5H), 5.08-5.00 (m, 3H), 3.87 (s, 1H), 2.78 (s, 1H), 2.24-2.15 (m, 1H), 2.14 (d, J=9.0 Hz, 1H), 1.97 (t, J=20.5 Hz, 1H), 1.71 (d, J=14.0 Hz, 1H).

Workup

  1. stirringthe mixture was stirred at 130° C. for another 2 hours
  2. customAfter being quenched with water (1 mL)
  3. additionthe mixture was diluted with ethyl acetate (300 mL)
  4. washwashed with saturated brine (3×50 mL)
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationconcentrated
  7. customThe residue was purified by silica gel chromatography
  8. washeluting with petroleum ether/ethyl acetate (4:1)

Sources & evidence

ORD record
ord-dca2b760f2f348418b7f3cc8d7c6ab43
Source dataset
uspto-grants-2014_04
Patent number
US08697715B2

Reaction notes

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