Sodium Azide → HCID 86607259, compound

HRID 1437379Notes

Reaction equation

HRID 1437379 reaction equation
[CH3:1][O:2][C:3]([C@@H:5]1[CH2:10][CH2:9][C@H:8](Br)[C@H:7]([OH:12])[CH2:6]1)=[O:4].[N-:13]=[N+:14]=[N-:15].[Na+]>CN(C=O)C>[CH3:1][O:2][C:3]([C@@H:5]1[CH2:10][CH2:9][C@@H:8]([N:13]=[N+:14]=[N-:15])[C@H:7]([OH:12])[CH2:6]1)=[O:4]

Participants

4

Reactant 2

HCID 33557Sodium AzideHCID 15640156HCID 15640156, compound

Product 1

HCID 86607259HCID 86607259, compoundYield 42%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
60 °C

Procedure

A solution of bromide (a) (52.4 g, 221 mmol) in DMF (1.2 liters) was treated with sodium azide (21.5 g, 331 mmol) and heated at 60° C. for 8 hours. The mixture was stirred at room temperature overnight and then evaporated. The residue was extracted with warm iso-propanol (2×300 ml). Evaporation afforded an oil which was chromatographed on silica eluting with a gradient of ethyl acetate in petroleum ether affording an oil (31 g) which was a 2:1 mixture of desired (1R,3R,4R)-4-azido-3-hydroxy-cyclohexanecarboxylic acid methyl ester to (R)-3-oxo-cyclohexanecarboxylic acid methyl ester. Further chromatography on silica eluting with a methanol/dichloromethane gradient afforded the desired intermediate as an oil (18.4 g, 42%)

Workup

  1. customevaporated
  2. extractionThe residue was extracted with warm iso-propanol (2×300 ml)
  3. customEvaporation
  4. customafforded an oil which
  5. customwas chromatographed on silica eluting with a gradient of ethyl acetate in petroleum ether affording an oil (31 g) which
  6. additiona 2:1 mixture of desired (1R,3R,4R)-4-azido-3-hydroxy-cyclohexanecarboxylic acid methyl ester to (R)-3-oxo-cyclohexanecarboxylic acid methyl ester

Sources & evidence

ORD record
ord-e62e2f416a004abb9819ab97cbc31bbb
Source dataset
uspto-grants-2009_11
Patent number
US07622481B2

Reaction notes

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