Ethyl Acetate → 2-({[Tert-butyl(diphenyl)silyl]oxy}methyl)-2,3-dihydronaphtho[1,2-b][1,4]oxathiine-5,6-dione

HRID 563122

Reaction equation

HRID 563122 reaction equation
[C:1]1(=[O:12])[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:4]=[CH:3][C:2]1=[O:11].[Si:13]([O:30][CH2:31][CH:32]([OH:35])[CH2:33][SH:34])([C:26]([CH3:29])([CH3:28])[CH3:27])([C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.C(N(C(C)C)CC)(C)C.C(OCC)(=O)C>C(#N)C>[Si:13]([O:30][CH2:31][CH:32]1[O:35][C:4]2[C:5]3[C:10]([C:1](=[O:12])[C:2](=[O:11])[C:3]=2[S:34][CH2:33]1)=[CH:9][CH:8]=[CH:7][CH:6]=3)([C:26]([CH3:29])([CH3:27])[CH3:28])([C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)[C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 106671,2-NaphthoquinoneHCID 81531DiisopropylethylamineHCID 212558771-t-BUTYLDIPHENYLSILYLOXY-3-MERCAPTO-2-PROPANOL

Product 1

HCID 252638602-({[Tert-butyl(diphenyl)silyl]oxy}methyl)-2,3-dihydronaphtho[1,2-b][1,4]oxathiine-5,6-dioneYield 187.4%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution of naphthalene-1,2-dione (0.103 g, 0.65 mmol) in acetonitrile (4.0 mL) was added 1-{[tert-butyl(diphenyl)silyl]oxy}-3-mercaptopropan-2-ol (0.226 g, 0.065 mmol) followed by diisopropylethylamine (0.114 mL, 0.065 mmol). The reaction mixture was stirred for 10 minutes at room temperature followed by addition of ethyl acetate (10 mL). The organic layer was washed with water (10 mL) and 1.0 N HCl (5 mL). The organic layer was dried with sodium sulfate and concentrated under reduced pressure. (ii) To the residue was added p-toluenesulfonic acid (0.48 g, mmol) followed by acetonitrile (5 mL). The reaction mixture was stirred at room temperature for 2 hours. To the reaction mixture was added ethyl acetate (10 mL) and the organic layer was extracted with water (10 mL). The organic layer was dried with sodium sulfate and concentrated under reduced pressure. The crude mixture was purified by flash column chromatography (SiO2, 100% dichloromethane) to give the product as a purple solid (0.061 g, 18%). M.p.=205-210° C.; 400 MHz 1H NMR (CDCl3) δ: 8.4-8.1 (m, 1H), 7.75-7.5 (m, 6H), 7.49-7.3 (m, 7H), 4.65-4.58 (m, 1H), 4.1-3.93 (m, 2H), 3.2-3.05 (m, 2H), 1.08 (s, 9H); LCMS: 501 [M+H].

Workup

  1. washThe organic layer was washed with water (10 mL) and 1.0 N HCl (5 mL)
  2. dry with materialThe organic layer was dried with sodium sulfate
  3. concentrationconcentrated under reduced pressure
  4. addition(ii) To the residue was added p-toluenesulfonic acid (0.48 g, mmol)
  5. stirringThe reaction mixture was stirred at room temperature for 2 hours
  6. additionTo the reaction mixture was added ethyl acetate (10 mL)
  7. extractionthe organic layer was extracted with water (10 mL)
  8. dry with materialThe organic layer was dried with sodium sulfate
  9. concentrationconcentrated under reduced pressure
  10. customThe crude mixture was purified by flash column chromatography (SiO2, 100% dichloromethane)

Sources & evidence

ORD record
ord-90af9ddd35f64401bb80ea755be8d968
Source dataset
uspto-grants-2011_11
Patent number
US08067459B2

Linked notes

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