Isopropanol → HCID 59226477, compound

HRID 2046809Notes

Reaction equation

HRID 2046809 reaction equation
[Si:1]([O:8][C@H:9]1[C@H:14]([O:15][Si:16]([C:19]([CH3:22])([CH3:21])[CH3:20])([CH3:18])[CH3:17])[C@@H:13]([CH3:23])[CH2:12][C:11]([C:24]2[CH:29]=[CH:28][N:27]=[CH:26][C:25]=2[N+:30]([O-])=O)=[CH:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].CC(O)C>C(O)C.CCOC(C)=O.[Pd].CCCCCCC>[Si:1]([O:8][C@@H:9]1[C@@H:14]([O:15][Si:16]([C:19]([CH3:21])([CH3:22])[CH3:20])([CH3:18])[CH3:17])[C@H:13]([CH3:23])[CH2:12][C@H:11]([C:24]2[CH:29]=[CH:28][N:27]=[CH:26][C:25]=2[NH2:30])[CH2:10]1)([C:4]([CH3:5])([CH3:6])[CH3:7])([CH3:3])[CH3:2].[Si:1]([O:8][C@H:9]1[C@H:14]([O:15][Si:16]([C:19]([CH3:21])([CH3:22])[CH3:20])([CH3:18])[CH3:17])[C@@H:13]([CH3:23])[CH2:12][C@@H:11]([C:24]2[CH:29]=[CH:28][N:27]=[CH:26][C:25]=2[NH2:30])[CH2:10]1)([C:4]([CH3:5])([CH3:6])[CH3:7])([CH3:3])[CH3:2]

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-butyldimethylsilyloxy)-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-6d43303161a543cbbd99ce0c1cd6c447
Source dataset
uspto-grants-2013_11
Patent number
US08592455B2

Reaction notes

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