Water → HCID 67704267, compound

HRID 2173007Notes

Reaction equation

HRID 2173007 reaction equation
[OH2:1].C[N+]1([O-])CCOCC1.C[N+]1([O-])CCOCC1.[C:18]([O:22][C:23]([NH:25][C@@:26]1([C:39]([O:41][C:42]([CH3:45])([CH3:44])[CH3:43])=[O:40])[CH:31]=[CH:30][C@@H:29]2[C@H:27]1[C@H:28]2[C:32]([O:34][C:35]([CH3:38])([CH3:37])[CH3:36])=[O:33])=[O:24])([CH3:21])([CH3:20])[CH3:19].CCCCCC.C(OCC)(=O)C.[OH2:58]>CC(C)=O.[Os](=O)(=O)(=O)=O>[C:18]([O:22][C:23]([NH:25][C@@:26]1([C:39]([O:41][C:42]([CH3:45])([CH3:44])[CH3:43])=[O:40])[C@H:31]([OH:1])[C@H:30]([OH:58])[C@@H:29]2[C@H:27]1[C@H:28]2[C:32]([O:34][C:35]([CH3:36])([CH3:38])[CH3:37])=[O:33])=[O:24])([CH3:21])([CH3:19])[CH3:20]

Participants

8

Reactant 5

HCID 962WaterHCID 82029Methyl morpholine oxideHCID 2724197N-Methylmorpholine N-oxide monohydrate2×HCID 21226206Ethyl acetate hexaneHCID 71681345Di-tert-butyl (1S,2S,5R,6S)-2-[(tert-butoxycarbonyl)amino]bicyclo[3.1.0]hex-3-ene-2,6-dicarboxylate

Product 1

HCID 67704267HCID 67704267, compoundYield 69%

Reagents, catalysts & solvents 2

HCID 30318Osmium TetroxideCatalystHCID 180AcetoneSolvent

Conditions

Temperature
23 °C

Procedure

Osmium tetraoxide (4% wt/wt in water, 231.78 mL, 241.05 g, 37.93 mmol,) is added at 23° C. to a solution of N-methylmorpholine-N-oxide hydrate (101.62 mL; 114.83 g, 424.78 mmol), N-methylmorpholine-N-oxide hydrate (116.88 g, 864.74 mmol), 4-methylmorpholine-4-oxide (198.88 mL; 195.50 g, 1.67 mol), and di-tert-butyl (1S,2S,5R,6S)-2-[(tert-butoxycarbonyl)amino]bicyclo[3.1.0]hex-3-ene-2,6-dicarboxylate (600.00 g, 1.52 mol) in acetone (12.00 L) and water (1.80 L). The mixture is stirred at 23° C. overnight. Thin layer chromatograph (hexane/ethyl acetate 3:2; stain: PMA) analysis of the reaction mixture revealed complete consumption of di-tert-butyl (1S,2S,5R,6S)-2-[(tert-butoxycarbonyl)amino]bicyclo[3.1.0]hex-3-ene-2,6-dicarboxylate. The reaction is quenched with saturated aqueous Na2S2O3 (1 L) and extracted with methyl tert-butyl ether (15 L). The organic phase is washed with an aqueous solution (1.5 L) prepared from 37% aqueous HCl (300 mL) and brine (1.2 L), dried with anhydrous MgSO4, filtered, and concentrated in vacuo. The residue is slurried in heptane (1.5 L), filtered, washed with heptane (2×500 mL), and resulting solid. The solid is dried under vacuum to yield the title compound (450 g, 69% yield).

Workup

  1. customconsumption of di-tert-butyl (1S,2S,5R,6S)-2-[(tert-butoxycarbonyl)amino]bicyclo[3.1.0]hex-3-ene-2,6-dicarboxylate
  2. customThe reaction is quenched with saturated aqueous Na2S2O3 (1 L)
  3. extractionextracted with methyl tert-butyl ether (15 L)
  4. washThe organic phase is washed with an aqueous solution (1.5 L)
  5. customprepared from 37% aqueous HCl (300 mL) and brine (1.2 L)
  6. dry with materialdried with anhydrous MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. filtrationfiltered
  10. washwashed with heptane (2×500 mL)
  11. customresulting solid
  12. customThe solid is dried under vacuum

Sources & evidence

ORD record
ord-0e3d50c5ec7e4e348f3c1d4ee1147fc7
Source dataset
uspto-grants-2015_06
Patent number
US09056844B2

Reaction notes

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