(Dimethyl sulfide)trihydroboron → Tert-butyl 7-oxa-3,10-diazaspiro[5.6]dodecane-3-carboxylate

HRID 471210Notes

Reaction equation

HRID 471210 reaction equation
B.CSC.O=[C:6]1[NH:24][CH2:23][CH2:22][C:9]2([CH2:14][CH2:13][N:12]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:11][CH2:10]2)[O:8][CH2:7]1>C1COCC1>[CH2:10]1[C:9]2([CH2:22][CH2:23][NH:24][CH2:6][CH2:7][O:8]2)[CH2:14][CH2:13][N:12]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:11]1

Participants

4

Reactant 2

HCID 12423031(Dimethyl sulfide)trihydroboronHCID 57989131Tert-butyl 9-oxo-7-oxa-3,10-diazaspiro[5.6]dodecane-3-carboxylate

Product 1

HCID 57989265Tert-butyl 7-oxa-3,10-diazaspiro[5.6]dodecane-3-carboxylate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
70 °C

Procedure

Borane-methyl sulfide complex (2M in THF, 2.88 mL) was added to a solution of tert-butyl 9-oxo-7-oxa-3,10-diazaspiro[5.6]dodecane-3-carboxylate (example 89, step d) (0.41 g) in dry THF (40 mL) and the reaction mixture then heated at 70° C. for 30 minutes under nitrogen. The mixture was cooled to room temperature and quenched with methanol. The solvents were removed under reduced pressure and the residue dissolved in methanol (100 mL). N1,N2-dimethylethane-1,2-diamine (1.0 g) was added and the mixture heated at reflux under nitrogen for 16 h. Further N1,N2-dimethylethane-1,2-diamine (1.0 g) was added and refluxing continued for 16 h. The solvents were evaporated under reduced pressure and the residue azeotroped with toluene. The crude product was purified by flash silica chromatography using 6% methanol in dichloromethane with 1% triethylamine as solvent. Pure fractions were evaporated to dryness to afford the subtitled compound. Yield 0.176 g.

Workup

  1. temperatureThe mixture was cooled to room temperature
  2. customquenched with methanol
  3. customThe solvents were removed under reduced pressure
  4. dissolutionthe residue dissolved in methanol (100 mL)
  5. additionN1,N2-dimethylethane-1,2-diamine (1.0 g) was added
  6. temperaturethe mixture heated
  7. temperatureat reflux under nitrogen for 16 h
  8. additionFurther N1,N2-dimethylethane-1,2-diamine (1.0 g) was added
  9. temperaturerefluxing
  10. customThe solvents were evaporated under reduced pressure
  11. customthe residue azeotroped with toluene
  12. customThe crude product was purified by flash silica chromatography
  13. customPure fractions were evaporated to dryness

Sources & evidence

ORD record
ord-97055bd2e86c45de8e0d406fab975648
Source dataset
uspto-grants-2014_01
Patent number
US08629271B2

Reaction notes

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