Lithium hydride → 1-(Methoxycarbonyl)-1-(tert-butoxycarbonyl)cyclopent-3-ene

HRID 1690818Notes

Reaction equation

HRID 1690818 reaction equation
[CH3:1][CH:2]([C:10]([O-:12])=[O:11])[C:3]([O:5][C:6]([CH3:9])([CH3:8])[CH3:7])=[O:4].[H-].[Li+].[CH3:15][CH:16]1N(C(N(C)C)=O)[CH2:17]1.Cl[CH2:25]/C=C\CCl>C1COCC1.O.CC(OC)(C)C>[CH3:25][O:11][C:10]([C:2]1([C:3]([O:5][C:6]([CH3:8])([CH3:7])[CH3:9])=[O:4])[CH2:17][CH:16]=[CH:15][CH2:1]1)=[O:12]

Participants

7

Reactant 4

HCID 62714Lithium hydrideHCID 64321151,4-Dichloro-cis-2-buteneHCID 11007919N,N,2-trimethylaziridine-1-carboxamideHCID 22457350t-Butyl methylmalonate

Product 1

HCID 669027691-(Methoxycarbonyl)-1-(tert-butoxycarbonyl)cyclopent-3-ene

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent3×HCID 23212559water MeOtBuSolvent

Conditions

Temperature
2.5 °C

Procedure

Add a solution of t-butyl methylmalonate (129 g, 0.75 mol) in THF (385 mL) to a slurry of LiH (14.9 g, 1.875 mol) in THF (900 mL) and N,N-dimethylpropylene urea (DMPU, 155 g, 1.2 mol) over 30 minutes while maintaining the temperature at 0-5° C. Heat the reaction mixture to 65° C. and add a solution of cis-1,4-dichloro-2-butene (95%, 100 g, 0.8 mol, 1.08 eq) in THF (100 mL) over 5.5 hours, maintaining the temperature at 63-67° C. Stir the reaction for 4 hours at 65° C. A water/MTBE work-up of the reaction mixture yields 1-(methoxycarbonyl)-1-(tert-butoxycarbonyl)cyclopent-3-ene.

Workup

  1. temperatureHeat the reaction mixture to 65° C.
  2. temperaturemaintaining the temperature at 63-67° C
  3. customthe reaction for 4 hours at 65° C

Sources & evidence

ORD record
ord-53cd703cdd564f3096fcb50286bad7b4
Source dataset
uspto-grants-2012_04
Patent number
US08153683B2

Reaction notes

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