Triethylamine → Benzyl [7-{N-(tert-butoxycarbonyl)amino}-3-(3-methoxy-4-nitrobenzoyl)-2-methylindolizin-1-yl]carboxylate

HRID 1987843Notes

Reaction equation

HRID 1987843 reaction equation
[C:1]([O:6][CH2:7][C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)(=[O:5])/[CH:2]=[CH:3]/[CH3:4].C(N(CC)CC)C.[Br-].[C:22]([O:26][C:27]([NH:29][C:30]1[CH:35]=[CH:34][N+:33]([CH2:36][C:37]([C:39]2[CH:44]=[CH:43][C:42]([N+:45]([O-:47])=[O:46])=[C:41]([O:48][CH3:49])[CH:40]=2)=[O:38])=[CH:32][CH:31]=1)=[O:28])([CH3:25])([CH3:24])[CH3:23]>CN(C)C=O.[O-2].[Mn+2]>[C:22]([O:26][C:27]([NH:29][C:30]1[CH:35]=[CH:34][N:33]2[C:32]([CH:31]=1)=[C:2]([C:1]([O:6][CH2:7][C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)=[O:5])[C:3]([CH3:4])=[C:36]2[C:37](=[O:38])[C:39]1[CH:44]=[CH:43][C:42]([N+:45]([O-:47])=[O:46])=[C:41]([O:48][CH3:49])[CH:40]=1)=[O:28])([CH3:25])([CH3:24])[CH3:23]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 5356259Benzyl crotonate, (E)-HCID 866075524-[N-(tert-butoxycarbonyl)amino]-1-[2-(3-methoxy-4-nitrophenyl)-2-oxoethyl]pyridinium bromide

Product 1

HCID 86607554Benzyl [7-{N-(tert-butoxycarbonyl)amino}-3-(3-methoxy-4-nitrobenzoyl)-2-methylindolizin-1-yl]carboxylateYield 44%

Reagents, catalysts & solvents 2

HCID 160959Manganese oxideCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
90 °C

Procedure

9.4 g (53.38 mmol) of benzyl crotonate, 1.8 mL (12.8 mmol) of triethylamine and 3.7 g (42.68 mmol) of manganese oxide are successively added to a solution of 5.0 g (10.67 mmol) of 4-[N-(tert-butoxycarbonyl)amino]-1-[2-(3-methoxy-4-nitrophenyl)-2-oxoethyl]pyridinium bromide in 40 mL of dimethylformamide. The reaction mixture is then heated at 90° C. for 4 hours and then filtered on a silica bed, eluting with ethyl acetate. The filtrate is poured over water and extracted with ethyl acetate. After decantation, the organic phase is washed with a saturated sodium chloride solution, dried over sodium sulfate and then concentrated under reduced pressure. The product is purified by chromatography on silica gel, eluting with a toluene/ethyl acetate (95/5 to 70/30) mixture. 2.6 g of an orange-coloured powder are obtained.

Workup

  1. filtrationfiltered on a silica bed
  2. washeluting with ethyl acetate
  3. additionThe filtrate is poured over water
  4. extractionextracted with ethyl acetate
  5. washAfter decantation, the organic phase is washed with a saturated sodium chloride solution
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customThe product is purified by chromatography on silica gel
  9. washeluting with a toluene/ethyl acetate (95/5 to 70/30) mixture

Sources & evidence

ORD record
ord-5eb3c09ddfb04067836c21f1cb978761
Source dataset
uspto-grants-2009_06
Patent number
US07553845B2

Reaction notes

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