Isopropanol → HCID 59226477, compound

HRID 2192581Notes

Reaction equation

HRID 2192581 reaction equation
[C:1]([Si:5]([CH3:32])([CH3:31])[O:6][C@H:7]1[C@H:12]([O:13][Si:14]([C:17]([CH3:20])([CH3:19])[CH3:18])([CH3:16])[CH3:15])[C@@H:11]([CH3:21])[CH2:10][C:9]([C:22]2[CH:27]=[CH:26][N:25]=[CH:24][C:23]=2[N+:28]([O-])=O)=[CH:8]1)([CH3:4])([CH3:3])[CH3:2].CC(O)C>C(O)C.CCOC(C)=O.[Pd].CCCCCCC>[Si:5]([O:6][C@@H:7]1[C@@H:12]([O:13][Si:14]([C:17]([CH3:19])([CH3:20])[CH3:18])([CH3:16])[CH3:15])[C@H:11]([CH3:21])[CH2:10][C@H:9]([C:22]2[CH:27]=[CH:26][N:25]=[CH:24][C:23]=2[NH2:28])[CH2:8]1)([C:1]([CH3:2])([CH3:3])[CH3:4])([CH3:32])[CH3:31].[Si:5]([O:6][C@H:7]1[C@H:12]([O:13][Si:14]([C:17]([CH3:19])([CH3:20])[CH3:18])([CH3:16])[CH3:15])[C@@H:11]([CH3:21])[CH2:10][C@@H:9]([C:22]2[CH:27]=[CH:26][N:25]=[CH:24][C:23]=2[NH2:28])[CH2:8]1)([C:1]([CH3:2])([CH3:3])[CH3:4])([CH3:32])[CH3:31]

Participants

7

Reactant 2

HCID 3776IsopropanolHCID 59226440HCID 59226440, compound

Product 2

HCID 59226477HCID 59226477, compoundHCID 68552774HCID 68552774, compound

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 8900HeptaneSolventHCID 21584252Ethanol ethylacetateSolvent

Procedure

To a solution of (+/−)-4-((3R,4R,5S)-3,4-bis(tert-butyldimethyl-silyloxy)-5-methylcyclohex-1-enyl)-3-nitropyridine (1.0 equiv.) in ethanol/EtOAc, at a concentration of 0.1 M, was added 10% palladium on carbon (0.1 eq.). The resultant heterogeneous solution was put under an atmosphere of hydrogen and was stirred for 14 hours. At this time the mixture was filtered through a pad of celite eluting with EtOAc. The volatiles were removed in vacuo and the crude material was purified by automated silica column chromatography (Rf=0.2, 40% EtOAc in Heptane) to yield pure racemic product. LCMS: MH+ 451.3, Rt=1.35 min. The racemic compound was resolved by chiral chromatography (IC column, 1 mL/min, 5% IPA in Heptane) to yield 4-((1S,3S,4S,5R)-3,4-bis(tert-butyldimethylsilyloxy)-5-methylcyclohexyl)pyridin-3-amine (6.01 min) and 4-((1R,3R,4R,5S)-3,4-bis(tert-butyldimethylsilyloxy)-5-methylcyclohexyl)pyridin-3-amine (8.34 min).

Workup

  1. filtrationAt this time the mixture was filtered through a pad of celite
  2. washeluting with EtOAc
  3. customThe volatiles were removed in vacuo
  4. customthe crude material was purified by automated silica column chromatography (Rf=0.2, 40% EtOAc in Heptane)
  5. customto yield pure racemic product

Sources & evidence

ORD record
ord-9ba8087431134f9ab9de00d0a64dd6c5
Source dataset
uspto-grants-2012_12
Patent number
US08329732B2

Reaction notes

Loading…