Potassium Hydroxide → 1-(2-Phenylhexahydro-2,5-methanopentalen-3a-yl)ethanone

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Reaction Steps

2-Methyl-5-phenyl-adamantan-2-ol (20 g, 82.6 mmol) obtained in step III, (86 g, 355.4 mmol), dissolved in a mixture of AcOH (76.3 mL) and THF (360 mL) was added dropwise via an addition funnel to the ice bath cooled NaOCl (4%, 3.5 L) solution over a period of 15 minutes. Solid n-Bu4NI (13.1 g, 35.6 mmol) was added and the reaction mixture was stirred for 1.5 h. The two layers were separated, the aqueous layer was extracted with diisopropylether and the combined organic layer was washed with water and brine, dried over Na2SO4, and the solvent was removed under reduced pressure. The residue was dissolved in methanol (165 mL), KOH (39.8 g, 300 mmol) was added, and the mixture was refluxed for 1 h. The solvent was evaporated under reduced pressure and the crude product was purified by column chromatography to yield compound 1-(1-phenyltricyclo[3.3.1.03,7]non-3-yl)ethanone (50.0 g) in 59% yield as viscous liquid. m/z (M+1) 241; IR (cm−1): 2924, 2867, 1697, 1445, 1356, 1223, 757, 699. 1H NMR (CDCl3) 300 MHz δ 7.38-7.19 (m, 5H), 2.86-2.80 (m, 1H), 2.59-2.50 (m, 1H), 2.32-2.25 (m, 1H), 2.23 (s, 3H), 2.10-1.99 (m, 4H), 1.90-1.79 (m, 4H), 1.78-1.71 (m, 1H). 13C NMR (CDCl3) 75 MHz δ, 211.7, 146.7, 128.2 (2C), 125.7 (2C), 124.7, 61.9, 50.2, 49.0, 47.9, 45.7, 42.4, 42.3, 37.6, 26.4.

Provenance & Evidence