{1-[Allyl-(2,4-dimethoxy-benzyl)-carbamoyl]-2,2-dimethyl-but-3-enyl}-carbamic acid tert-butyl ester → [1-(2,4-dimethoxy-benzyl)-4,4-dimethyl-2-oxo-2,3,4,7-tetrahydro-1H-azepin-3-yl]-carbamic acid tert-butyl ester

HRID 852013Notes

Reaction equation

HRID 852013 reaction equation
[C:1]([O:5][C:6](=[O:31])[NH:7][CH:8]([C:14](=[O:30])[N:15]([CH2:27][CH:28]=C)[CH2:16][C:17]1[CH:22]=[CH:21][C:20]([O:23][CH3:24])=[CH:19][C:18]=1[O:25][CH3:26])[C:9]([CH3:13])([CH3:12])[CH:10]=C)([CH3:4])([CH3:3])[CH3:2]>ClCCl>[C:1]([O:5][C:6](=[O:31])[NH:7][CH:8]1[C:9]([CH3:12])([CH3:13])[CH:10]=[CH:28][CH2:27][N:15]([CH2:16][C:17]2[CH:22]=[CH:21][C:20]([O:23][CH3:24])=[CH:19][C:18]=2[O:25][CH3:26])[C:14]1=[O:30])([CH3:2])([CH3:3])[CH3:4]

Participants

3

Reactant 1

HCID 69507319{1-[Allyl-(2,4-dimethoxy-benzyl)-carbamoyl]-2,2-dimethyl-but-3-enyl}-carbamic acid tert-butyl ester

Product 1

HCID 69492432[1-(2,4-dimethoxy-benzyl)-4,4-dimethyl-2-oxo-2,3,4,7-tetrahydro-1H-azepin-3-yl]-carbamic acid tert-butyl esterYield 63%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

{1-[Allyl-(2,4-dimethoxy-benzyl)-carbamoyl]-2,2-dimethyl-but-3-enyl}-carbamic acid tert-butyl ester (0.5 g, 1.16 mmol) was dissolved in dichloromethane (400 ml), bis(tricyclohexylphosphine)benzylidine ruthenium dichloride (145 mg, 0.17 mmol) was added and the purple solution was refluxed for 48 hours. The solvent was evaporated, the residue was dissolved in ethyl acetate and washed with NaHCO3 solution, 1M KHSO4 solution and brine. After drying with magnesiumsulfate the organic layer was concentrated and purified by flash chromatography (heptane/ethyl acetate=4:1) to yield 295 mg (63%) of [1-(2,4-dimethoxy-benzyl)-4,4-dimethyl-2-oxo-2,3,4,7-tetrahydro-1H-azepin-3-yl]-carbamic acid tert-butyl ester; MS: m/e=405.5 (MH+).

Workup

  1. temperaturethe purple solution was refluxed for 48 hours
  2. customThe solvent was evaporated
  3. dissolutionthe residue was dissolved in ethyl acetate
  4. washwashed with NaHCO3 solution, 1M KHSO4 solution and brine
  5. dry with materialAfter drying with magnesiumsulfate the organic layer
  6. concentrationwas concentrated
  7. custompurified by flash chromatography (heptane/ethyl acetate=4:1)

Sources & evidence

ORD record
ord-e309c5dc82d14993aa345b645064711d
Source dataset
uspto-grants-2007_08
Patent number
US07253158B2

Reaction notes

Loading…