Methyl morpholine oxide → HCID 66634692, compound

HRID 878790Notes

Reaction equation

HRID 878790 reaction equation
C=[C:2]1[C:17]2[C:9](=[CH:10][C:11]3[O:12][CH2:13][O:14][C:15]=3[CH:16]=2)[CH:8]([C:18]2[CH:23]=[C:22]([O:24][CH3:25])[C:21]([O:26][CH3:27])=[C:20]([O:28][CH3:29])[CH:19]=2)[C@H:7]2[C@@H:3]1[CH2:4][O:5][C:6]2=[O:30].C[N+]1([O-])CC[O:35]CC1>ClCCl.[Os](=O)(=O)(=O)=O>[CH3:25][O:24][C:22]1[CH:23]=[C:18]([CH:8]2[C:9]3[C:17](=[CH:16][C:15]4[O:14][CH2:13][O:12][C:11]=4[CH:10]=3)[C:2](=[O:35])[C@@H:3]3[C@H:7]2[C:6](=[O:30])[O:5][CH2:4]3)[CH:19]=[C:20]([O:28][CH3:29])[C:21]=1[O:26][CH3:27]

Participants

5

Reactant 2

HCID 82029Methyl morpholine oxideHCID 56928333HCID 56928333, compound

Product 1

HCID 66634692HCID 66634692, compoundYield 125.2%

Reagents, catalysts & solvents 2

HCID 30318Osmium TetroxideCatalystHCID 6344DichloromethaneSolvent

Procedure

(11S,15S)-16-Methylidene-10-(3,4,5-trimethoxyphenyl)-4,6,13-trioxatetracyclo[7.7.0.0^{3,7}.0^{11,15}]hexadeca-1,3(7),8-trien-12-one obtained in Example 1 (0.730 g, 1.22 mmol) and N-methyl morpholine oxide (50 wt-% solution in water, 1.25. mL, 5.34 mmol) were suspended in dichloromethane (60 mL). Osmium tetroxide (4 wt-% solution in water, 0.37 mL, 0.060 mmol) was added to the suspension. The mixture was stirred vigorously at rt. After most of starting material had been consumed (over week-end), NalO4 (0.52 g, 2.44 mmol) was added and the reaction was stirred for an additional 30 min. The reaction was quenched by addition of aqueous sodium thiosulfate (50 mL) and the phases were separated. The aqueous phase was extracted with dichloromethane (2×50 mL) and the combined organic layers were washed with brine, dried over Na2SO4, filtered and evaporated to give 630 mg (85% yield) of the product in 75% purity. Another batch of ketone has been purified by filtration through a pad of silica topped with celite and eluting with Heptane:EtOAc 1:1. LCMS: ACE 3 C8, 50×3.0 mm, 10% to 97% acetonitrile in 0.1% TFA in water, 1 mL/min; Rt=2.091.

Workup

  1. customAfter most of starting material had been consumed (over week-end), NalO4 (0.52 g, 2.44 mmol)
  2. additionwas added
  3. stirringthe reaction was stirred for an additional 30 min
  4. customThe reaction was quenched by addition of aqueous sodium thiosulfate (50 mL)
  5. customthe phases were separated
  6. extractionThe aqueous phase was extracted with dichloromethane (2×50 mL)
  7. washthe combined organic layers were washed with brine
  8. dry with materialdried over Na2SO4
  9. filtrationfiltered
  10. customevaporated

Sources & evidence

ORD record
ord-27a1901e00a84a4a9b15dee2619faf25
Source dataset
uspto-grants-2015_03
Patent number
US08987475B2

Reaction notes

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