Hydrogen Peroxide → 4'-hydroxy-2,3-dihydrospiro[furo[2,3-g][1,4]benzodioxine-8,3'-indol]-2'(1'H)-one

HRID 1965778Notes

Reaction equation

HRID 1965778 reaction equation
Br[C:2]1[CH:10]=[CH:9][CH:8]=[C:7]2[C:3]=1[C:4]1([C:22]3[C:13](=[CH:14][C:15]4[O:20][CH2:19][CH2:18][O:17][C:16]=4[CH:21]=3)[O:12][CH2:11]1)[CH2:5][NH:6]2.C([Li])(C)(C)C.B(OC)(OC)[O:29]C.OO.[OH2:37]>O1CCCC1>[OH:37][C:2]1[CH:10]=[CH:9][CH:8]=[C:7]2[C:3]=1[C:4]1([C:22]3[C:13](=[CH:14][C:15]4[O:20][CH2:19][CH2:18][O:17][C:16]=4[CH:21]=3)[O:12][CH2:11]1)[C:5](=[O:29])[NH:6]2

Participants

7

Reactant 5

HCID 784Hydrogen PeroxideHCID 962WaterHCID 8470Trimethyl borateHCID 685993684'-Bromo-1,2,2',3-tetrahydrospiro[furo[2,3-g][1,4]benzodioxine-8,3'-indole]HCID 178418306HCID 178418306, compound

Product 1

HCID 593523524'-hydroxy-2,3-dihydrospiro[furo[2,3-g][1,4]benzodioxine-8,3'-indol]-2'(1'H)-oneYield 2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 4′-bromo-1′,2,2′,3-tetrahydrospiro[furo[2,3-g][1,4]benzodioxine-8,3′-indole] (0.30 g, 0.80 mmol) in anhydrous tetrahydrofuran (20 mL) at −98° C. was added tert-butyllithium (1.90 mL, 1.7 M solution in pentane, 3.2 mmol) and stirred for 15 min. Trimethyl borate (0.36 mL, 3.2 mmol) was added and the reaction mixture was allowed to warm to ambient temperature and stirred for 16 h. A solution of hydrogen peroxide in water (0.28 mL, 35% w/w, 3.2 mmol) was added to the reaction mixture at 0° C., and the mixture was allowed to warm to ambient temperature, stirred for 0.5 h and concentrated in vacuo. The residue was triturated with water and filtered. The resultant solid was purified by column chromatography and eluted with a 0% to 50% gradient of ethyl acetate in dichloromethane to afford 4′-hydroxy-2,3-dihydrospiro[furo[2,3-g][1,4]benzodioxine-8,3′-indol]-2′(1′H)-one (0.004 g, 2%) as a colorless solid: mp>250° C.; 1H NMR (300 MHz, DMSO-d6) δ 10.37 (s, 1H), 9.50 (s, 1H), 7.00 (dd, J=8.0, 8.0 Hz, 1H), 6.39-6.34 (m, 3H), 6.08 (s, 1H), 4.64 (ABq, 2H), 4.09 (m, 4H); 13C NMR (75 MHz, DMSO-d6) δ 179.3, 155.5, 154.1, 144.0, 143.6, 137.7, 130.1, 121.0, 116.1, 111.1, 110.5, 101.8, 98.7, 76.8, 64.6, 64.0, 57.2; MS (ES+) m/z 311.7 (M+1).

Workup

  1. stirringstirred for 16 h
  2. temperatureto warm to ambient temperature
  3. stirringstirred for 0.5 h
  4. concentrationconcentrated in vacuo
  5. customThe residue was triturated with water
  6. filtrationfiltered
  7. customThe resultant solid was purified by column chromatography
  8. washeluted with a 0% to 50% gradient of ethyl acetate in dichloromethane

Sources & evidence

ORD record
ord-9e915f1e6bb847ddbbbee1075514f06d
Source dataset
uspto-grants-2013_04
Patent number
US08415370B2

Reaction notes

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