Selenium Dioxide → HCID 23433604, compound

HRID 2121753Notes

Reaction equation

HRID 2121753 reaction equation
[C:1]([O:5][C:6]([N:8]1[C:17]2[C:12](=[CH:13][C:14]([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)=[CH:15][CH:16]=2)[C:11]([CH3:24])=[CH:10][C:9]1([CH3:26])[CH3:25])=[O:7])([CH3:4])([CH3:3])[CH3:2].[Se](=O)=[O:28]>O1CCOCC1>[C:1]([O:5][C:6]([N:8]1[C:17]2[C:12](=[CH:13][C:14]([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)=[CH:15][CH:16]=2)[C:11]([CH2:24][OH:28])=[CH:10][C:9]1([CH3:26])[CH3:25])=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

4

Reactant 2

HCID 24007Selenium DioxideHCID 23433558HCID 23433558, compound

Product 1

HCID 23433604HCID 23433604, compoundYield 23.1%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

A solution of N-tert-butyloxycarbonyl-1,2-dihydro-2,2,4-trimethyl-6-phenyl quinoline (structure 10, where R1=phenyl) (310 mg, 0.888 mmol) and selenium dioxide (345 mg, 3.11 mmol) in 17 mL of dioxane was heated to reflux for 3 h. The reaction mixture was quenched with 1:1 NaS2O3 (10%)/Na2HCO3 (10%), extracted with dichloromethane, dried (MgSO4), and the organic phase was concentrated in vacuo. Purification by flash chromatography (silica gel, hexane/ethyl acetate, 4:1) gave 212 mg of the intermediate aldehyde along with 75 mg of the desired alcohol of structure 11, where R1=phenyl. The aldehyde was treated with sodium borohydride in 25 mL of methanol at 0° C. After 1 h at 0° C., the reaction mixture was quenched with water, extracted with ethyl acetate and concentrated in vacuo to give an oil that was purified by flash chromatography (silica gel, hexane/ethyl acetate, 4:1) providing structure 11, where R1=phenyl (240 mg, 84%). 1H NMR (acetone d6) 7.68 (d, J=9, 2H), 7.61 (d, J=1.8, 1H), 7.47 (dd, J=6.2, 1.8, 1H), 7.41 (d, J=6.4, 2H), 7.29 (m, 2H), 5.80 (s, 1H), 4.51 (d, J=6.8, 2H), 4.12 (t, J=6.8, 1H), 1.52 (br s, 15H).

Workup

  1. temperatureto reflux for 3 h
  2. customThe reaction mixture was quenched with 1:1 NaS2O3 (10%)/Na2HCO3 (10%)
  3. extractionextracted with dichloromethane
  4. dry with materialdried (MgSO4)
  5. concentrationthe organic phase was concentrated in vacuo
  6. customPurification by flash chromatography (silica gel, hexane/ethyl acetate, 4:1)

Sources & evidence

ORD record
ord-4647726f68674064a4f23e2884d65c0a
Source dataset
uspto-grants-2004_02
Patent number
US06696459B1

Reaction notes

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