(4R,9aR)-6-hydroxymethyl-4-methyl-3,4,9,9a-tetrahydro-1H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester → (4R,9aR)-6-Formyl-4-methyl-3,4,9,9a-tetrahydro-1 H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester

HRID 1985714Notes

Reaction equation

HRID 1985714 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:20][C@@H:19]([CH3:21])[N:18]2[C@H:10]([CH2:11][C:12]3[C:17]2=[N:16][C:15]([CH2:22][OH:23])=[CH:14][CH:13]=3)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]>ClCCl.[O-2].[O-2].[Mn+4]>[C:1]([O:5][C:6]([N:8]1[CH2:20][C@@H:19]([CH3:21])[N:18]2[C@H:10]([CH2:11][C:12]3[C:17]2=[N:16][C:15]([CH:22]=[O:23])=[CH:14][CH:13]=3)[CH2:9]1)=[O:7])([CH3:3])([CH3:2])[CH3:4]

Participants

4

Reactant 1

HCID 67238448(4R,9aR)-6-hydroxymethyl-4-methyl-3,4,9,9a-tetrahydro-1H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester

Product 1

HCID 86596361(4R,9aR)-6-Formyl-4-methyl-3,4,9,9a-tetrahydro-1 H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl esterYield 80.5%

Reagents, catalysts & solvents 2

HCID 178418406HCID 178418406, compoundCatalystHCID 6344DichloromethaneSolvent

Procedure

To a solution of 2.00 g (4R,9aR)-6-Hydroxymethyl-4-methyl-3,4,9,9a-tetrahydro-1H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester in 20 ml dichloromethane was added 6.00 g manganese dioxide in 3 portions of 2.00 g in intervals of 1 h at room temperature while stirring. The reaction mixture was stirred for 2 more hours at room temperature. The solids were removed by filtration over dicalite and the mother liquor was evaporated and the residue was purified by chromatography on silica gel with heptane:ethyl acetate=1:1 to yield 1.600 g of the title compound as slightly yellow crystals (MS: 316.0 (M+H+))

Workup

  1. stirringThe reaction mixture was stirred for 2 more hours at room temperature
  2. customThe solids were removed by filtration over dicalite
  3. customthe mother liquor was evaporated
  4. customthe residue was purified by chromatography on silica gel with heptane

Sources & evidence

ORD record
ord-cabd267508bf4af8aa1c4693cace436f
Source dataset
uspto-grants-2009_06
Patent number
US07547699B2

Reaction notes

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