Dimethyl Carbonate → Methyl 1-benzyl-2-oxoazepane-3-carboxylate

HRID 467470Notes

Reaction equation

HRID 467470 reaction equation
[CH2:1]([N:8]1[CH2:14][CH2:13][CH2:12][CH2:11][CH2:10][C:9]1=[O:15])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Li+].CC([N-]C(C)C)C.[C:24](=O)([O:27]C)[O:25][CH3:26]>CCOCC>[CH2:1]([N:8]1[CH2:14][CH2:13][CH2:12][CH2:11][CH:10]([C:24]([O:25][CH3:26])=[O:27])[C:9]1=[O:15])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 12021Dimethyl CarbonateHCID 14910681-Benzylazepan-2-oneHCID 2724682Lithium diisopropylamide

Product 1

HCID 21902024Methyl 1-benzyl-2-oxoazepane-3-carboxylate

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

A cooled (−78° C.) solution of 1-2 (2 g, 9.84 mmol) in Et2O (50 ml) was treated with LDA (9.84 ml, 19.68 mmol) and stirred for 1 h. The mixture was treated with dimethyl carbonate (1.658 ml, 19.68 mmol), warmed to RT and stirred overnight. The mixture was quenched with 1N HCl and extracted twice with EtOAc. The organic phase was dried over Na2SO4, filtered and concentrated. The crude material was purified by gradient elution on silica gel (0 to 60% EtOAc in Hex) to yield a 1:1 mixture of 1-3 and starting material as a tan oil. Data for 1-3: LRMS m/z (M+H): 262.1.

Workup

  1. stirringstirred overnight
  2. customThe mixture was quenched with 1N HCl
  3. extractionextracted twice with EtOAc
  4. dry with materialThe organic phase was dried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe crude material was purified by gradient elution on silica gel (0 to 60% EtOAc in Hex)
  8. customto yield
  9. additiona 1:1 mixture of 1-3

Sources & evidence

ORD record
ord-41e3d9850e4744a88b246d49586fed64
Source dataset
uspto-grants-2014_01
Patent number
US08623863B2

Reaction notes

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