Methyl morpholine oxide → (NE)-N-[2-[1-[tert-butyl(dimethyl)silyl]oxy-3-methylcyclobutyl]ethylidene]-2-methylpropane-2-sulfinamide

HRID 1009158Notes

Reaction equation

HRID 1009158 reaction equation
[CH2:1]([C:4]1([O:9][Si:10]([C:13]([CH3:16])([CH3:15])[CH3:14])([CH3:12])[CH3:11])[CH2:7][CH:6]([CH3:8])[CH2:5]1)[CH:2]=C.C[N+]1([O-])CCOCC1.I([O-])(=O)(=O)=O.[Na+].[CH3:31][C:32]([S@:35]([NH2:37])=[O:36])([CH3:34])[CH3:33]>CC(O)(C)C.O.C1COCC1.O.[Os](=O)(=O)(=O)=O>[Si:10]([O:9][C:4]1([CH2:1]/[CH:2]=[N:37]/[S:35]([C:32]([CH3:34])([CH3:33])[CH3:31])=[O:36])[CH2:5][CH:6]([CH3:8])[CH2:7]1)([C:13]([CH3:14])([CH3:15])[CH3:16])([CH3:11])[CH3:12]

Participants

8

Reactant 4

HCID 82029Methyl morpholine oxideHCID 10964479tert-Butylsulfinamide, (R)-(+)-HCID 23667635Sodium periodateHCID 67304682(1-Allyl-3-methylcyclobutoxy)(tert-butyl)dimethylsilane

Product 1

HCID 87349189(NE)-N-[2-[1-[tert-butyl(dimethyl)silyl]oxy-3-methylcyclobutyl]ethylidene]-2-methylpropane-2-sulfinamide

Reagents, catalysts & solvents 3

HCID 30318Osmium TetroxideCatalystHCID 962WaterSolventHCID 22124471t-Butanol tetrahydrofuran waterSolvent

Procedure

(1-Allyl-3-methylcyclobutoxy)(tert-butyl)dimethylsilane (4.1000 g, 17.05 mmol) was dissolved in 150 ml of t-BuOH/H2O/THF (2/2/1) and osmium tetroxide (10.84 ml, 0.8525 mmol, 2.5 wt %) and 4-methylmorpholine oxide (2.996 g, 25.58 mmol) were added. The mixture was stirred for 6 h and the mixture was diluted with 250 ml water and extracted with EtOAc. The combined organic extracts were evaporated and re-dissolved in 150 ml of t-BuOH/H2O/THF (2/2/1). Sodium periodate (4.741 g, 22.17 mmol) was added and stirring was continued for 6 h. The mixture was filtered and diluted with 250 ml of water. The mixture was extracted with Et2O and the combined organic extracts were dried over MgSO4, evaporated and re-dissolved in 100 ml CH2Cl2. Cupric sulfate anhydrous (8.164 g, 51.15 mmol), and (r)-(+)-2-methyl-2-propanesulfinamide (4.133 g, 34.10 mmol) were added at RT and stirring was continued over night. The reaction was filtered and hydrolyzed with 30 ml water. The mixture was extracted 3×EtOAc (3×150 ml) and the combined organic extracts were dried over MgSO4 and evaporated. Glass col. chrom. (20-50% EtOAc in Hex) provided (E)-N-(2-(1-(tert-butyldimethylsilyloxy)-3-methylcyclobutyl)ethylidene)-2-methylpropane-2-sulfinamide. Mixture of cis/trans at the cyclobutylring (4:1).

Workup

  1. extractionextracted with EtOAc
  2. customThe combined organic extracts were evaporated
  3. dissolutionre-dissolved in 150 ml of t-BuOH/H2O/THF (2/2/1)
  4. stirringstirring
  5. waitwas continued for 6 h
  6. filtrationThe mixture was filtered
  7. additiondiluted with 250 ml of water
  8. extractionThe mixture was extracted with Et2O
  9. dry with materialthe combined organic extracts were dried over MgSO4
  10. customevaporated
  11. dissolutionre-dissolved in 100 ml CH2Cl2
  12. stirringstirring
  13. waitwas continued over night
  14. filtrationThe reaction was filtered
  15. extractionThe mixture was extracted 3×EtOAc (3×150 ml)
  16. dry with materialthe combined organic extracts were dried over MgSO4
  17. customevaporated

Sources & evidence

ORD record
ord-e1421dd555de4f5a9740ee5b40371b85
Source dataset
uspto-grants-2011_07
Patent number
US07973047B2

Reaction notes

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