Benzyl Alcohol → tert-Butyl (S)-3-{[(benzyloxy)carbonyl]amino}-4-oxo-4,6,7,8-tetrahydropyrrolo[1,2-a]pyrimidine-6-carboxylate

HRID 10955Notes

Reaction equation

HRID 10955 reaction equation
[C:1]([O:5][C:6]([C@H:8]1[N:12]2[C:13](=[O:20])[C:14](C(O)=O)=[CH:15][N:16]=[C:11]2[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C([N:23]([CH2:26]C)CC)C.C1C=CC(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:35])=CC=1.[CH2:45]([OH:52])[C:46]1[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=1>O1CCOCC1>[CH2:45]([O:52][C:26]([NH:23][C:14]1[C:13](=[O:20])[N:12]2[C@H:8]([C:6]([O:5][C:1]([CH3:2])([CH3:3])[CH3:4])=[O:7])[CH2:9][CH2:10][C:11]2=[N:16][CH:15]=1)=[O:35])[C:46]1[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=1

Participants

6

Reactant 4

HCID 244Benzyl AlcoholHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 54474487(S)-6-(tert-Butoxycarbonyl)-4-oxo-4,6,7,8-tetrahydropyrrolo[1,2-a]pyrimidine-3-carboxylic acid

Product 1

HCID 54224046tert-Butyl (S)-3-{[(benzyloxy)carbonyl]amino}-4-oxo-4,6,7,8-tetrahydropyrrolo[1,2-a]pyrimidine-6-carboxylateYield 73%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

A solution of carboxylic acid 1f (11.4 g, 40.7 mmol), triethylamine (5.67 mL, 40.7 mmol), and DPPA (8.86 mL, 40.7 mmol) in 180 mL 1,4-dioxane was heated at reflux for 2 h. Benzyl alcohol (4.67 mL, 45 mmol) was added and the mixture was heated at reflux for an additional 3 h. The mixture was concentrated in vacuo and the oil obtained was purified by flash chromatography (50 to 100% EtOAc/hexanes) to provide 11.13 g (73%) of the benzyl carbamate (1 g) as a tan solid. 1H NMR (300 MHz, CDCl3) δ 8.67 (br s, 1H), 7.39–7.34 (m, 5H), 5.21 (s, 2H), 4.98 (dd, J=9.6, 3.0, 1H), 3.23–2.98 (m, 2H), 2.63–2.49 (m, 1H), 2.37–2.23 (m, 1H), 1.48 (s, 9H).

Workup

  1. temperatureat reflux for 2 h
  2. temperaturethe mixture was heated
  3. temperatureat reflux for an additional 3 h
  4. concentrationThe mixture was concentrated in vacuo
  5. customthe oil obtained
  6. customwas purified by flash chromatography (50 to 100% EtOAc/hexanes)

Sources & evidence

ORD record
ord-834073e0ca044b46a874997ac8390157
Source dataset
uspto-grants-2006_08
Patent number
US07094783B2

Reaction notes

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