Methyl 3-bromoprop-2-ynoate → 7-Tert-butyl 2-methyl 3-bromo-7-azabicyclo[2.2.1]hepta-2,5-diene-2,7-dicarboxylate

HRID 1852728

Reaction equation

HRID 1852728 reaction equation
[Br:1][C:2]#[C:3][C:4]([O:6][CH3:7])=[O:5].[N:8]1([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH:12]=[CH:11][CH:10]=[CH:9]1>>[Br:1][C:2]1[CH:9]2[N:8]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH:12]([CH:11]=[CH:10]2)[C:3]=1[C:4]([O:6][CH3:7])=[O:5]

Participants

3

Reactant 2

HCID 294619Methyl 3-bromoprop-2-ynoateHCID 643494tert-butyl 1H-pyrrole-1-carboxylate

Product 1

HCID 152851047-Tert-butyl 2-methyl 3-bromo-7-azabicyclo[2.2.1]hepta-2,5-diene-2,7-dicarboxylate

Conditions

Temperature
95 °C

Procedure

Into a 2000-mL 3-necked round-bottom flask was placed methyl 3-bromopropiolate (120 g, 736.33 mmol, 1.00 equiv) and tert-butyl 1H-pyrrole-1-carboxylate (615.61 g, 3.68 mol, 5.00 equiv). The resulting solution was stirred for 30 hr at 95° C. in an oil bath. The reaction mixture was cooled and distilled under reduced pressure (20 mm Hg). The fraction collected at 55° C. was purified by silica gel chromatography (ethyl acetate/petroleum ether, 1:20) to afford 7-tert-butyl 2-methyl 3-bromo-7-azabicyclo[2.2.1]hepta-2,5-diene-2,7-dicarboxylate as a yellow liquid.

Workup

  1. customInto a 2000-mL 3-necked round-bottom flask was placed
  2. temperatureThe reaction mixture was cooled
  3. distillationdistilled under reduced pressure (20 mm Hg)
  4. customThe fraction collected at 55° C.
  5. customwas purified by silica gel chromatography (ethyl acetate/petroleum ether, 1:20)

Sources & evidence

ORD record
ord-5bfe9bb8f26f42d98e705ac70cac6df6
Source dataset
uspto-grants-2015_02
Patent number
US08962611B2

Linked notes

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