Sodium Carbonate → tert-Butyl cyclopropyl{3-formyl-5-[(1E)-3-methoxy-1-propen-1-yl]benzyl}carbamate

HRID 337635Notes

Reaction equation

HRID 337635 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:17]=[C:18]([CH:20]=[O:21])[CH:19]=1)[CH2:5][N:6]([CH:14]1[CH2:16][CH2:15]1)[C:7](=[O:13])[O:8][C:9]([CH3:12])([CH3:11])[CH3:10].CC1(C)C(C)(C)OB(/[CH:30]=[CH:31]/[CH2:32][O:33][CH3:34])O1.C([O-])([O-])=O.[Na+].[Na+]>CN(C=O)C.O>[CH:14]1([N:6]([CH2:5][C:4]2[CH:3]=[C:2](/[CH:30]=[CH:31]/[CH2:32][O:33][CH3:34])[CH:19]=[C:18]([CH:20]=[O:21])[CH:17]=2)[C:7](=[O:13])[O:8][C:9]([CH3:12])([CH3:11])[CH3:10])[CH2:16][CH2:15]1

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 162174432-[(1E)-3-methoxyprop-1-en-1-yl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 86651677tert-Butyl (3-bromo-5-formylbenzyl)cyclopropylcarbamate

Product 1

HCID 86651678tert-Butyl cyclopropyl{3-formyl-5-[(1E)-3-methoxy-1-propen-1-yl]benzyl}carbamate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
90 °C

Procedure

To a solution of tert-butyl (3-bromo-5-formylbenzyl)cyclopropylcarbamate (1 eq.) from the previous step and 4,4,5,5-tetramethyl-2-[(1E)-3-(methyloxy)-1-propen-1-yl]-1,3,2-dioxaborolane (1 eq.) in DMF (0.2 M) was added trans-bis(triphenylphosphine) palladium(II) bromide (0.05 eq.). The vessel was repeatedly evacuated and back-filled with nitrogen. Finally, 2 M aq. Na2CO3 (3 eq.) was added and the resulting mixture was heated at 90° C. for 6 h. The now black suspension was cooled to RT, diluted with water and extracted with ether. The combined organic extracts were washed further with 10% aq. HCl, 1 N aq. NaOH, water and brine, dried over Na2SO4, filtered and the filtrate concentrated in vacuo. Purification of the crude product by way of flash chromatography (SiO2, Hex→3:7 (v/v) Hex:EtOAc) afforded the title compound as a pale yellow oil.

Workup

  1. customThe vessel was repeatedly evacuated
  2. additionback-filled with nitrogen
  3. temperatureThe now black suspension was cooled to RT
  4. extractionextracted with ether
  5. washThe combined organic extracts were washed further with 10% aq. HCl, 1 N aq. NaOH, water and brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationthe filtrate concentrated in vacuo
  9. customPurification of the crude product by way of flash chromatography (SiO2, Hex→3:7 (v/v) Hex:EtOAc)

Sources & evidence

ORD record
ord-353ffb6ad4284a8c9c6fbdf4d5179f22
Source dataset
uspto-grants-2014_11
Patent number
US08889714B2

Reaction notes

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