Cyclohexene → HCID 45094652, compound

Participants

Reaction Conditions

Reaction Steps

A 0° C. solution of 1-(2-ethylpyrazolo[1,5-a]pyridin-3-yl)ethanone (1.33 g, 7.1 mmol) in THF (20.0 mL) was treated with 1.0M THF solution of ethyl magnesium bromide (9.0 mL, 9.0 mmol). The reaction was allowed to warm to room temperature and stirred for 2.5 hours. An additional amount of ethyl magnesium bromide (2.0 mL, 2.0 mmol) was added and the reaction stirred for 1.5 hours. The reaction was quenched with 2N HCl then extracted with ethyl acetate, washed with brine, dried over MgSO4 and filtered. The filtrate was concentrated in vacuo to dryness. The residue was subjected to column chromatography (20% ethyl acetate/heptane) to give 0.55 g (39%) of a yellow oil as a 4:1 mixture of the regio-isomers of 2-ethyl-3-[(1Z)-1-methylprop-1-enyl]pyrazolo[1,5-a]pyridine and 2-ethyl-3-(1-ethylvinyl)pyrazolo[1,5-a]pyridine. The mixture (0.22 mg, 1.1 mmol) was placed in a flask with cyclohexene (8.0 mL), 10% palladium on carbon (0.05 g) and AICl3 (0.016 g) and heated to 85° C. for 39 hours. The reaction was cooled to room temperature and filtered through diatomaceous earth. The filtrate was concentrated in vacuo to dryness. The residue was subjected to column chromatography (20% ethyl acetate/heptane) to give 0.19 g (86%) of a clear oil as the title compound: 1H NMR (400 MHz, CDCl3) δ 8.36 (d, J=7.0 Hz, 1H), 7.45 (d, J=9.0 Hz, 1H), 7.00–6.96 (m, 1H), 6.64–6.60 (m, 1H), 2.93–2.82 (m, 3H), 1.83–1.74 (m, 2H), 1.40–1.33 (m, 6H), 0.87 (t, J=7.4 Hz, 3H); MS (EI) m/z 203.1 (M++H).

Provenance & Evidence