Hydrochloric Acid → Bicyclo[2.2.1]hept-5-ene-2,3-diol-, (exo,exo)-

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Reaction Steps

A 1-L round bottom flask was charged under nitrogen with 450 mL of tert-butanol, 30 mL pyridine, 92 g (1 mol) of norbornadiene, 257.4 g of a 50% aqueous solution of 4-methylmorpholine-N-oxide (Sigma-Aldrich Chemical Company, Milwaukee, Wis.) and 6 mL of a 4% aqueous solution of osmium tetroxide (Sigma-Aldrich Chemical Company). This mixture was heated at reflux overnight. The solution was cooled to room temperature and treated with 3 g of sodium hydrosulfite and 30 g of Florisil. The pH of the solution was adjusted to 7 by addition of aqueous HCl. The mixture was stirred and filtered through Celite. The filtrate was concentrated on a rotary evaporator to remove most of the organic solvents. The remaining solution was acidified to pH 1-2 and extracted with ether. The ether extracts were washed with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated to give 65.3 g (52%) of the desired product as a white solid judged sufficiently pure for subsequent transformation. Another sample prepared by the same procedure had 1H-NMR (ppm, CDCl3, major isomer): δ 1.60 (1H, dp, J=9.5, 2.0 Hz), 1.87 (1H, d, J=9.0 Hz), 2.67 (2H, p, J=2.0 Hz), 3.68 (2H, d, J=2.0 Hz), 6.01 (2H, t, J=2.0 Hz). 13C—NMR (ppm, CDCl3, major isomer): δ 42.4, 48.2, 69.1, 136.6. (Exo/exo isomer to endolendo isomer ratio was 97:3 by 1H-NMR analysis.)

Provenance & Evidence