Cyclohexanone → HCID 70979874, compound

HRID 1749106Notes

Reaction equation

HRID 1749106 reaction equation
[C:1]([O:5][C:6](=[O:30])[N:7]([C:19]1[CH:24]=[CH:23][C:22]([N+:25]([O-])=O)=[C:21]([C:28]#[N:29])[N:20]=1)[CH2:8][C:9]1[CH:14]=[CH:13][C:12]([O:15][CH3:16])=[CH:11][C:10]=1[O:17][CH3:18])([CH3:4])([CH3:3])[CH3:2].[C:31]1(=O)[CH2:36][CH2:35][CH2:34][CH2:33][CH2:32]1.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].C([O-])(O)=O.[Na+]>C1COCC1.C(O)(=O)C.ClCCCl.[Pd]>[C:1]([O:5][C:6](=[O:30])[N:7]([C:19]1[CH:24]=[CH:23][C:22]([NH2:25])=[C:21]([CH2:28][NH:29][CH:31]2[CH2:36][CH2:35][CH2:34][CH2:33][CH2:32]2)[N:20]=1)[CH2:8][C:9]1[CH:14]=[CH:13][C:12]([O:15][CH3:16])=[CH:11][C:10]=1[O:17][CH3:18])([CH3:4])([CH3:3])[CH3:2]

Participants

9

Reactant 4

HCID 7967Cyclohexanone2×HCID 516892Sodium BicarbonateHCID 5049666Sodium triacetoxyborohydrideHCID 70980218HCID 70980218, compound

Product 1

HCID 70979874HCID 70979874, compound

Reagents, catalysts & solvents 4

HCID 23938PalladiumCatalystHCID 111,2-DichloroethaneSolventHCID 176Acetic AcidSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of (6-cyano-5-nitro-pyridin-2-yl)-(2,4-dimethoxy-benzyl)-carbamic acid tert-butyl ester Example 20 (Step 2) (1.10 g, 2.65 mmol, 1 equiv) and cyclohexanone (320 μL, 3.20 mmol, 1.2 equiv) in THF (10 mL) and acetic acid (20 mL), was added Pd/C (10%, 200 mg) and the reaction mixture was hydrogenated overnight. The catalyst was removed by filtration and the filtrate evaporated to give an oil. The oil was dissolved in DCE (15 mL) and treated with cyclohexanone (100 μL, 1.0 mmol) followed by sodium triacetoxyborohydride (954 mg, 4.5 mmol, 1.7 equiv). The reaction mixture was stirred at ambient temperature for 2 h, saturated NaHCO3 was added and the product was extracted with dichloromethane. The organic phase was dried (MgSO4), filtered and the solvent evaporated. The crude material was purified by column chromatography (SiO2, eluted with dichloromethane—MeOH 0-10%) to afford (5-amino-6-cyclohexylaminomethyl-pyridin-2-yl)-(2,4-dimethoxy-benzyl)-carbamic acid tert-butyl ester (390 mg). MS: [M+H]+=471.

Workup

  1. customThe catalyst was removed by filtration
  2. customthe filtrate evaporated
  3. customto give an oil
  4. extractionthe product was extracted with dichloromethane
  5. dry with materialThe organic phase was dried (MgSO4)
  6. filtrationfiltered
  7. customthe solvent evaporated
  8. customThe crude material was purified by column chromatography (SiO2, eluted with dichloromethane—MeOH 0-10%)

Sources & evidence

ORD record
ord-522f03eaadf9449aa5d57b2d88f0b746
Source dataset
uspto-grants-2015_10
Patent number
US09155743B2

Reaction notes

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