Benzyl chloroformate → HCID 86691270, compound

HRID 2037296Notes

Reaction equation

HRID 2037296 reaction equation
Cl.[CH2:2]([O:4][C:5]([C@:7]1([NH2:19])[CH2:12][C:11](=[O:13])[C@@H:10]2[C@H:8]1[C@H:9]2[C:14]([O:16][CH2:17][CH3:18])=[O:15])=[O:6])[CH3:3].C(=O)([O-])[O-].[K+].[K+].Cl[C:27]([O:29][CH2:30][C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1)=[O:28]>O1CCCC1.C(OCC)(=O)C.O>[CH2:30]([O:29][C:27]([NH:19][C@@:7]1([C:5]([O:4][CH2:2][CH3:3])=[O:6])[CH2:12][C:11](=[O:13])[C@@H:10]2[C@H:8]1[C@H:9]2[C:14]([O:16][CH2:17][CH3:18])=[O:15])=[O:28])[C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1

Participants

7

Reactant 3

HCID 10387Benzyl chloroformateHCID 11430Potassium CarbonateHCID 86691271HCID 86691271, compound

Product 1

HCID 86691270HCID 86691270, compoundYield 99%

Reagents, catalysts & solvents 3

HCID 962WaterSolvent2×HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

Suspend diethyl-(1S,2S,5R,6R)-2-amino-4-oxo-bicyclo[3.1.0]hexane-2,6-dicarboxylate-hydrochloride (55.0 g, 188.5 mmol) in tetrahydrofuran (220 mL), then add water (220 mL) and potassium carbonate (92.1 g, 659.9 mmol). Stir the resulting mixture for 30 minutes. Add benzyl chloroformate (26.7 mL, 175.3 mmol) to the mixture over 45 minutes, keeping the reaction temperature below 25° C. Stir reaction mixture for 30 minutes, then dilute with ethyl acetate (550 mL) and water (275 mL). Separate the phases and back extract the aqueous layer with ethyl acetate (250 mL). Combine the organics and wash it sequentially with aqueous HCl (0.5N, 100 mL), saturated NaHCO3 (100 mL) and brine (100 mL). Dry the organic solution over Na2SO4, filter and concentrate in vacuo to afford the title compound as a clear oil (67.6 g, 92.1%). 1H NMR (CDCl3) δ 1.24-1.26 (m, 6H), 2.36 (bs, 1H), 2.47 (dd, 1H), 2.78 (dd, 1H), 2.90 (dd, 1H), 4.09-4.19 (m, 4H), 5.08 (s, 2H), 5.73 (s, 1H), 7.24-7.36 (m, 5H).

Workup

  1. customthe reaction temperature below 25° C
  2. stirringStir
  3. customreaction mixture for 30 minutes
  4. customSeparate the phases
  5. extractionback extract the aqueous layer with ethyl acetate (250 mL)
  6. washCombine the organics and wash it sequentially with aqueous HCl (0.5N, 100 mL), saturated NaHCO3 (100 mL) and brine (100 mL)
  7. dry with materialDry the organic solution over Na2SO4
  8. filtrationfilter
  9. concentrationconcentrate in vacuo

Sources & evidence

ORD record
ord-73ad15fa74764bb68a9f8594dd875b65
Source dataset
uspto-grants-2013_11
Patent number
US08575214B2

Reaction notes

Loading…