Acetic Acid → tert-butyl (3R,4R,5S)-1-(3-aminopyridin-4-yl)-4-(tert-butyldimethylsilyloxy)-5-methylpiperidin-3-ylcarbamate

HRID 924430Notes

Reaction equation

HRID 924430 reaction equation
[Si:1]([O:8][C@@H:9]1[C@@H:14]([CH3:15])[CH2:13][N:12]([C:16]2[CH:21]=[CH:20][N:19]=[CH:18][C:17]=2[N+:22]([O-])=O)[CH2:11][C@H:10]1[NH:25][C:26](=[O:32])[O:27][C:28]([CH3:31])([CH3:30])[CH3:29])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].CC(O)=O>CCOC(C)=O.[Fe]>[NH2:22][C:17]1[CH:18]=[N:19][CH:20]=[CH:21][C:16]=1[N:12]1[CH2:13][C@H:14]([CH3:15])[C@@H:9]([O:8][Si:1]([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2])[C@H:10]([NH:25][C:26](=[O:32])[O:27][C:28]([CH3:31])([CH3:30])[CH3:29])[CH2:11]1

Participants

5

Reactant 2

HCID 176Acetic AcidHCID 59226604tert-butyl (3R,4R,5S)-4-(tert-butyldimethylsilyloxy)-5-methyl-1-(3-nitropyridin-4-yl)piperidin-3-ylcarbamate

Product 1

HCID 59226553tert-butyl (3R,4R,5S)-1-(3-aminopyridin-4-yl)-4-(tert-butyldimethylsilyloxy)-5-methylpiperidin-3-ylcarbamateYield 510.6%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of tert-butyl [(3R,4R,5S)-4-{[tert-butyl(dimethyl)silyl]oxy}-5-methyl-1-(3-nitropyridin-4-yl)piperidin-3-yl]carbamate (130 mg, 0.279 mmol), AcOH (10.0 mL, 176 mmol) and iron powder (558 mg, 1.00 mmol) was stirred at room temperature for 2 h. The mixture was diluted with 30 mL of EtOAc and filtered through a pad of diatomaceous earth and the filtrate was then concentrated under reduced pressure. The resulting residue was diluted with EtOAc and then washed with aq. Na2CO3 solution and 0.2 M NaOH. The organic extract was concentrated under reduced pressure to give 0.622 g of the sub-title compound as a brown solid. LCMS calc. for C22H41N4O3Si (M+H)+: m/z=437.3. found: 437.1.

Workup

  1. filtrationfiltered through a pad of diatomaceous earth
  2. concentrationthe filtrate was then concentrated under reduced pressure
  3. additionThe resulting residue was diluted with EtOAc
  4. washwashed with aq. Na2CO3 solution and 0.2 M NaOH
  5. extractionThe organic extract
  6. concentrationwas concentrated under reduced pressure

Sources & evidence

ORD record
ord-ac8eed765ca74bcfa9f4d0d143c3a82b
Source dataset
uspto-grants-2016_03
Patent number
US09278950B2

Reaction notes

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