Diethyl Oxalate → HCID 124026306, compound

HRID 2203666Notes

Reaction equation

HRID 2203666 reaction equation
[Si:1]([O:18][CH:19]1[CH2:24][CH:23]2[CH:21]([CH:22]2[C:25](=[O:27])[CH3:26])[CH2:20]1)([C:14]([CH3:17])([CH3:16])[CH3:15])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[C:38](OCC)(=[O:44])[C:39]([O:41][CH2:42][CH3:43])=[O:40]>O1CCCC1>[Si:1]([O:18][CH:19]1[CH2:24][CH:23]2[CH:21]([CH:22]2[C:25](=[O:27])[CH2:26][C:38](=[O:44])[C:39]([O:41][CH2:42][CH3:43])=[O:40])[CH2:20]1)([C:14]([CH3:17])([CH3:16])[CH3:15])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 7268Diethyl OxalateHCID 2733832Lithium HexamethyldisilazideHCID 1189941801-(3-((tert-Butyldiphenylsilyl)oxy)bicyclo[3.1.0]hexan-6-yl)ethanone

Product 1

HCID 124026306HCID 124026306, compoundYield 117.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 1-(3-((tert-butyldiphenylsilyl)oxy)bicyclo[3.1.0]hexan-6-yl)ethanone (27 g, 71 mmol) in anhydrous tetrahydrofuran (300 mL) was added lithium bis(trimethylsilyl)amide (106 mL, 106 mmol, 1 M in tetrahydrofuran) slowly at −78° C. under nitrogen. After 0.5 h, diethyl oxalate (15.63 g, 107.0 mmol) was added, and the reaction mixture was warmed to room temperature. After 6 h, the reaction mixture was quenched with 3 M aqueous hydrochloric acid until the solution reached pH ˜3. The mixture was extracted with ethyl acetate (2×200 mL). The combined organics were washed with saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, filtered, and concentrated to provided ethyl 4-(3-((tert-butyldiphenylsilyl)oxy)bicyclo[3.1.0]hexan-6-yl)-2,4-dioxobutanoate as an orange solid (40 g), which was used without further purification. LCMS: [M+H]+ 479.0, [M+Na]+ 501.0, [M+Na+CH3CN]+ 542.0.

Workup

  1. waitAfter 6 h
  2. customthe reaction mixture was quenched with 3 M aqueous hydrochloric acid until the solution
  3. extractionThe mixture was extracted with ethyl acetate (2×200 mL)
  4. washThe combined organics were washed with saturated aqueous sodium chloride solution
  5. dry with materialdried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-a1e3bcd68ef64de3ac2010e7fd9f0d81
Source dataset
uspto-grants-2016_06
Patent number
US09365583B2

Reaction notes

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