tert-Butanol → 6,7,8,9-Tetrahydro-5H-6,9-methanocyclohepta[b]pyridine-7,8-diol

Participants

Reaction Steps

3-Aza-tricyclo[7.2.1.02,7]dodeca-2(7),3,5,10-tetraene (960 mg, 6.1 mmol) and trimethylamine N-oxide dihydrate (748 mg, 6.73 mmol) were stirred in dichloromethane (15 mL) and treated with osmium tetroxide (OsO4, 0.2 mL of a 15 mol % t-butanol solution) and the mixture was stirred vigorously. After 18 h, the residue was poured onto a silica gel column (2×6 inch) and eluted with hexanes (100 mL) then EtOAc to elute product as an oil that crystallizes on standing (1.16 g, 100%). (TLC EtOAc Rf 0.17); 1H NMR (400 MHz, CDCl3) δ 8.12 (d, J=4.9 Hz, 1H), 7.40 (d, J=7.5 Hz, 1H), 7.07 (dd, J=7.5, 4.9 Hz, 1H), 4.19 (d, J=6.0 Hz, 1H), 3.90 (d, J=6.0 Hz, 1H), 3.45 (s, 1H), 3.00 (dd, J=17.3, 4.8 Hz, 1H), 2.67 (d, J=17.3 Hz, 1H), 2.43 (m, 2H), 1.59 (d, J=11.6 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 159.4, 147.6, 138.1, 130.9, 122.3, 77.1, 75.4, 51.6, 42.2, 33.9, 28.5; APCl MS m/z 192.1 (M)+.

Provenance & Evidence