Dimethyl acetylenedicarboxylate → HCID 11109638, compound

HRID 1425912Notes

Reaction equation

[N:1]1([C:6]([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7])[CH:5]=[CH:4][CH:3]=[CH:2]1.[C:13]([O:21][CH3:22])(=[O:20])[C:14]#[C:15][C:16]([O:18][CH3:19])=[O:17]>[Al+3].[Cl-].[Cl-].[Cl-].C(Cl)Cl.CO>[C@@H:2]12[N:1]([C:6]([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7])[C@@H:5]([CH:4]=[CH:3]1)[C:15]([C:16]([O:18][CH3:19])=[O:17])=[C:14]2[C:13]([O:21][CH3:22])=[O:20]

Participants

Conditions

Temperature: 70 °C

Procedure

A mixture of tert-butyl 1H-pyrrole-1-carboxylate (XLV) (3.50 g 20.93 mmol), dimethyl but-2-ynedioate (XLVI) (2.57 mL, 20.93 mmol) and AlCl3 (28 mg, 0.21 mmol) were stirred for 3 days at 70° C. The crude product was purified by silica gel chromatography using 100% DCM then DCM/MeOH 1000/1→500/1 to give (1R,4S)-7-tert-butyl 2,3-dimethyl 7-azabicyclo[2.2.1]hepta-2,5-diene-2,3,7-tricarboxylate (XLVII) as a yellow oil (3.41 g, 11.04 mmol, 53% yield). 1H NMR (CDCl3) δ ppm 1.40 (s, 9H), 3.80 (s, 6H), 5.44 (s, 2H), 7.13 (d, J=13 Hz, 2H); ESIMS found for C15H19NO6 m/z 332 (M+Na).

Workup

customThe crude product was purified by silica gel chromatography

Sources & evidence

ORD record: ord-18cea04f8e7841ca8ee812f3756008e4
Source dataset: uspto-grants-2015_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08933018B2

Reaction notes

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