Cesium carbonate → tert-Butyl 4-formylnaphthalen-1-ylcarbamate

HRID 1641274Notes

Reaction equation

HRID 1641274 reaction equation
[C:1]([O:5][C:6](=[O:8])[NH2:7])([CH3:4])([CH3:3])[CH3:2].[CH:9](B(O)O)=[CH:10][CH2:11][CH2:12][CH2:13][CH3:14].[C:18](=[O:21])([O-])[O-].[Cs+].[Cs+].I([O-])(=O)(=O)=O.[Na+]>O1CCOCC1.C(O)(C)(C)C.[Os](=O)(=O)(=O)=O.C(OCC)(=O)C.O>[C:1]([O:5][C:6](=[O:8])[NH:7][C:9]1[C:14]2[C:13](=[CH:9][CH:10]=[CH:11][CH:12]=2)[C:12]([CH:18]=[O:21])=[CH:11][CH:10]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

10

Reactant 4

HCID 10796Cesium carbonateHCID 77922tert-Butyl carbamateHCID 2773444Hex-1-enylboronic AcidHCID 23667635Sodium periodate

Product 1

HCID 58745967tert-Butyl 4-formylnaphthalen-1-ylcarbamateYield 39.8%

Reagents, catalysts & solvents 5

HCID 30318Osmium TetroxideCatalystHCID 962WaterSolventHCID 6386tert-ButanolSolvent2×HCID 8857Ethyl AcetateSolvent2×HCID 312751,4-DioxaneSolvent2×

Procedure

4-Bromo-naphthalen-1-yl)-carbamic acid tert-butyl ester (3.669 g, 11.4 mmol), 1-hexeneylboronic acid (2.18 g, 17.1 mmol), cesium carbonate (7.4 g, 22.8 mmol) and tetrakistriphenylphosphine palladium(0) (50 mg) in dioxane (35 ml) are heated to 100° C. under a nitrogen atmosphere for 24 hours. The mixture is then cooled to room temperature and poured into ethyl acetate (300 ml) and washed with water (2×200 ml). The ethyl acetate layer is dried over anhydrous sodium sulfate and evaporated to dryness. The residue is taken up in dioxane (40 mol), t-butanol (40 ml) and water (10 ml) and osmium tetroxide 2.5%wt in t-butanol (0.1 ml) added. Sodium periodate (10 g) is then added in portions over 15 mins and the mixture allowed to stir at room temperature for 24 hours. The mixture is then poured into ethyl acetate (250 ml) and washed with water (300 ml). The ethyl acetate layer is dried over anhydrous sodium sulfate and evaporated to dryness. The residue is purified by column chromatography on silica gel eluted with 7.5% ethyl acetate in hexanes to give (4-formyl-naphthalen-1-yl)-carbamic acid tert-butyl ester as a light brown solid (923 mg). 1H NMR 300 MHz (CDCl3) 10.25(s, 1H), 9.4(d, 1H, J=8.7 Hz), 8.35(d, 1H, J=5.7 Hz), 7.95(d, 1H, J=5.7 Hz), 7.9(d, 1H, J=8.7 Hz), 7.6-7.75(m 2H), 7.3(s, 1H), 1.5(s, 9H).

Workup

  1. washwashed with water (2×200 ml)
  2. dry with materialThe ethyl acetate layer is dried over anhydrous sodium sulfate
  3. customevaporated to dryness
  4. washwashed with water (300 ml)
  5. dry with materialThe ethyl acetate layer is dried over anhydrous sodium sulfate
  6. customevaporated to dryness
  7. customThe residue is purified by column chromatography on silica gel
  8. washeluted with 7.5% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-8237bbf2600b4bdbb04830a325ae02a3
Source dataset
uspto-grants-2012_02
Patent number
US08114873B2

Reaction notes

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