Methane → Benzyl 4-hydroxy-4-methyltetrahydrofuran-3-ylcarbamate

HRID 877672Notes

Reaction equation

HRID 877672 reaction equation
[CH3:1]COCC.C[Mg]Br.[O:9]=[C:10]1[CH2:14][O:13][CH2:12][CH:11]1[NH:15][C:16](=[O:25])[O:17][CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.C>O1CCCC1>[OH:9][C:10]1([CH3:1])[CH2:14][O:13][CH2:12][CH:11]1[NH:15][C:16](=[O:25])[O:17][CH2:18][C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1

Participants

6

Reactant 4

HCID 297MethaneHCID 3283Diethyl EtherHCID 18523485Benzyl (4-oxotetrahydrofuran-3-yl)carbamateHCID 178418573HCID 178418573, compound

Product 1

HCID 68291164Benzyl 4-hydroxy-4-methyltetrahydrofuran-3-ylcarbamate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A 3 M ether solution of methylmagnesium bromide (4.07 mL, 12.20 mmol) was added dropwise to a solution of benzyl 4-oxotetrahydrofuran-3-ylcarbamate (1.305 g, 5.55 mmol, from Step 3) in tetrahydrofuran (50 mL) at 0° C. Gas evolution was observed during the addition, indicating formation of methane. After 1 h at 0° C., the mixture was quenched with saturated ammonium chloride (75 mL) and extracted with ethyl acetate three times. The combined extracts were dried (MgSO4) and concentrated. Silica gel chromatography, eluting with 20-70% ethyl acetate in hexanes, gave impure material. 1H NMR showed presence of the desired product. The impure material was combined with the material from another run (from 2.18 g of ketone starting material) and taken to the next reaction without purification.

Workup

  1. additionGas evolution was observed during the addition
  2. customthe mixture was quenched with saturated ammonium chloride (75 mL)
  3. extractionextracted with ethyl acetate three times
  4. dry with materialThe combined extracts were dried (MgSO4)
  5. concentrationconcentrated
  6. washSilica gel chromatography, eluting with 20-70% ethyl acetate in hexanes
  7. customgave impure material

Sources & evidence

ORD record
ord-e30f9fcb50104e1297496b80cacee92f
Source dataset
uspto-grants-2015_03
Patent number
US08987268B2

Reaction notes

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