(Dimethyl sulfide)trihydroboron → HCID 59822294, compound

HRID 1670517Notes

Reaction equation

HRID 1670517 reaction equation
B.CSC.[C:5]([O:9][C:10]([N:12]1[CH2:18][CH2:17][C:16]2[C:19]([C:24]#[N:25])=[C:20]([Cl:23])[CH:21]=[CH:22][C:15]=2[CH2:14][CH2:13]1)=[O:11])([CH3:8])([CH3:7])[CH3:6]>C1COCC1>[NH2:25][CH2:24][C:19]1[C:16]2[CH2:17][CH2:18][N:12]([C:10]([O:9][C:5]([CH3:7])([CH3:6])[CH3:8])=[O:11])[CH2:13][CH2:14][C:15]=2[CH:22]=[CH:21][C:20]=1[Cl:23]

Participants

4

Reactant 2

HCID 12423031(Dimethyl sulfide)trihydroboronHCID 59822282HCID 59822282, compound

Product 1

HCID 59822294HCID 59822294, compoundYield 81%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Add borane-methyl sulfide complex (40 mL, 80 mmol, 2M solution in THF) to a solution of 3-tert-butoxycarbonyl-7-chloro-6-cyano-2,3,4,5-tetrahydro-1H-benzo[d]azepine (4.79 g, 10.2 mmol) in anhydrous THF (120 mL). Reflux the mixture overnight under nitrogen. Cool the mixture to room temperature and quench with methanol. Add KHSO4 (20 g in water) and stir for 1 h. Remove the organic solvent in vacuo and basify by addition of solid K2CO3. Extract with DCM and wash with brine. Collect the organic layer, dry over anhydrous Na2SO4, filter and concentrate in vacuo. Purify by chromatography on silica gel eluting with hexane/EtOAc (1:0 and 3:1), DCM and DCM/(chloroform:methanol:concentrated ammonium hydroxide 88:18: 2) (20:1, 10:1 and 5:1) to give the title compound (2.56 g, 81% over 2 steps). MS (ES+) m/z: 311 (M+H)+.

Workup

  1. temperatureReflux the mixture overnight under nitrogen
  2. customquench with methanol
  3. customRemove the organic solvent in vacuo
  4. additionbasify by addition of solid K2CO3
  5. extractionExtract with DCM
  6. washwash with brine
  7. customCollect the organic layer
  8. dry with materialdry over anhydrous Na2SO4
  9. filtrationfilter
  10. concentrationconcentrate in vacuo
  11. customPurify by chromatography on silica gel eluting with hexane/EtOAc (1:0 and 3:1), DCM and DCM/(chloroform:methanol:concentrated ammonium hydroxide 88:18: 2) (20:1, 10:1 and 5:1)

Sources & evidence

ORD record
ord-80f0401036244344ae8bb876a00de810
Source dataset
uspto-grants-2011_08
Patent number
US07994163B2

Reaction notes

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