Potassium Carbonate → HCID 57826940, compound

HRID 422583Notes

Reaction equation

HRID 422583 reaction equation
Br[C:2]1[CH:6]=[CH:5][S:4][C:3]=1[NH:7][C:8](=[O:14])[O:9][C:10]([CH3:13])([CH3:12])[CH3:11].C([O-])([O-])=O.[K+].[K+].Br[CH:22]([CH3:29])/[CH:23]=[CH:24]/[C:25]([O:27][CH3:28])=[O:26].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>CN(C=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(Cl)Cl>[CH3:28][O:27][C:25](=[O:26])[CH2:24][C:23]1[C:2]2[CH:6]=[CH:5][S:4][C:3]=2[N:7]([C:8]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:14])[C:22]=1[CH3:29]

Participants

8

Reactant 4

HCID 11430Potassium CarbonateHCID 11776TriphenylphosphineHCID 12882384HCID 12882384, compoundHCID 14143864tert-Butyl (3-bromothiophen-2-yl)carbamate

Product 1

HCID 57826940HCID 57826940, compoundYield 36.3%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of tert-butyl 3-bromothiophen-2-ylcarbamate (1 g, 3.59 mmol) in DMF (15 mL) was added K2CO3 (1.987 g, 14.38 mmol) and (E)-methyl 4-bromopent-2-enoate (prepared according to C. Girard et al, TL, vol 30, No. 52, pp 7399-7402, 1989) (1.388 g, 7.19 mmol). The reaction mixture was stirred at ambient temperature for 16 h. Palladium(II) acetate (0.040 g, 0.180 mmol) and PPh3 (0.094 g, 0.359 mmol) were added and the reaction mixture was heated to 85° C. for 18 h. DCM was added and the resulting solution was washed with water. The layers were separated and the organic solution was dried over MgSO4, filtered, and concentrated under reduced pressure. The crude material was purified by flash chromatography on silica gel (heptane/EtOAc: 95/5 to 55/45) to give the title compound (0.404 g, 36.3%): LC/MS (Table 1, Method d) Rt=2.40 min; MS m/z 310 (M+H)+; 1H NMR (CDCl3) δ 6.97 (m, 2H), 3.72 (s, 3H), 3.62 (s, 2H), 2.56 (s, 3H), 1.70 (s, 9H).

Workup

  1. customprepared
  2. temperaturethe reaction mixture was heated to 85° C. for 18 h
  3. washthe resulting solution was washed with water
  4. customThe layers were separated
  5. dry with materialthe organic solution was dried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customThe crude material was purified by flash chromatography on silica gel (heptane/EtOAc: 95/5 to 55/45)

Sources & evidence

ORD record
ord-2eecda8965744386aba57abd9fc9b871
Source dataset
uspto-grants-2012_01
Patent number
US08101645B2

Reaction notes

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