1,8-Diazabicyclo(5.4.0)undec-7-ene → (Z)-methyl2-(tert-butoxycarbonyl)-3-(2,2-dimethylbenzo[d][1,3]dioxol-5-yl)acrylate

HRID 1697193Notes

Reaction equation

HRID 1697193 reaction equation
[C:1]([O:5][C:6]([CH:8](P(OC)(OC)=O)[C:9]([O:11][CH3:12])=[O:10])=[O:7])([CH3:4])([CH3:3])[CH3:2].C1CCN2C(=NCCC2)CC1.[CH3:30][C:31]1([CH3:42])[O:35][C:34]2[CH:36]=[CH:37][C:38]([CH:40]=O)=[CH:39][C:33]=2[O:32]1>C(Cl)Cl.[Cl-].[NH4+]>[C:1]([O:5][C:6](/[C:8](=[CH:40]\[C:38]1[CH:37]=[CH:36][C:34]2[O:35][C:31]([CH3:42])([CH3:30])[O:32][C:33]=2[CH:39]=1)/[C:9]([O:11][CH3:12])=[O:10])=[O:7])([CH3:2])([CH3:3])[CH3:4]

Participants

6

Reactant 3

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 5960122,2-Dimethylbenzo[d][1,3]dioxole-5-carbaldehydeHCID 86599651Methyl2-(tert-butoxycarbonyl)-2-(dimethoxyphosphoryl)acetate

Product 1

HCID 67163448(Z)-methyl2-(tert-butoxycarbonyl)-3-(2,2-dimethylbenzo[d][1,3]dioxol-5-yl)acrylateYield 88.9%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent3×HCID 25517Ammonium ChlorideSolvent

Procedure

To a solution of methyl 2-(tert-butoxycarbonyl)-2-(dimethoxyphosphoryl)acetate (5255 mg, 17678 μmol) in 25 mL of DCM at 0° C. was added DBU (2665 μl, 17678 μmol) dropwise. To the mixture was then added a solution of 2,2-dimethylbenzo[d][1,3]dioxole-5-carbaldehyde (3000 mg, 16836 μmol) in 10 mL of DCM over 5 minutes so as to maintain internal temperature below 10° C. The reaction was warmed to rt and stirred overnight before being diluted with DCM (25 mL) and poured in saturated ammonium chloride (100 mL). The aqueous layer was extracted with DCM (1×50 mL). The combined organic layers were washed with 10% aqueous sodium bicarbonate then water then brine and dried over Na2SO4. Concentration under reduced pressure and purification by silica gel provided (Z)-methyl 2-(tert-butoxycarbonyl)-3-(2,2-dimethylbenzo[d][1,3]dioxol-5-yl)acrylate (5005 mg, 85.1% yield) as a white solid.

Workup

  1. temperatureto maintain internal temperature below 10° C
  2. extractionThe aqueous layer was extracted with DCM (1×50 mL)
  3. washThe combined organic layers were washed with 10% aqueous sodium bicarbonate
  4. dry with materialwater then brine and dried over Na2SO4
  5. concentrationConcentration
  6. customunder reduced pressure and purification by silica gel

Sources & evidence

ORD record
ord-44bb08ac66d14757915485544031ed27
Source dataset
uspto-grants-2012_04
Patent number
US08163909B2

Reaction notes

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