Reaction Steps
A solution of magnesium triflate (0.40 g, 1.23 mmol) in dry THF (5 mL) was added to a stirred solution under N2 of 3-phenyl-1,5-dioxaspiro[3.2]hexane (0.20 g, 1.23 mmol) in dry THF (2 mL). The temperature was then lowered to 0° C., and a solution of 1H-1,2,4-triazole (0.22 g, 1.48 mmol) in dry THF (10 mL) was added dropwise. The reaction mixture was stirred at 0° C. for 2.5 hours, warmed to room temperature and stirred for an additional 3 hours. Then, the mixture was concentrated to provide a yellow oil, which was purified by flash chromatography on silica gel (CH2Cl2/methanol 99.5:0.5 to 99:1). 2-Hydroxymethyl-3-phenyl-2-(1,2,4-triazol-1-yl)oxetane was isolated as an oil which was a 2:1 mixture of diastereomers (0.13 g, 45%): IR (film) 3403, 2903, 1499, 1279, 702 cm−1; Major diastereomer: 1H NMR (400 MHz, CDCl3) δ 8.18 (s, 1H), 8.11 (s, 1H), 7.40 (m, 5H), 5.11 (m, 1H), 5.06 (m, 1H), 4.74 (dd, J=16.3, 8.4 Hz, 1H), 3.94 (d, J=12.8 Hz, 1H), 3.83 (d, J=12.8 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 133.3, 129.0, 127.9, 127.7, 127.4, 127.4, 98.5, 68.9, 63.7, 48.7. Minor diastereomer: 1H NMR (400 MHz, CDCl3) δ 8.42 (s, 1H), 7.67 (s, 1H), 7.12 (m, 5H), 5.11 (m, 1H), 5.06 (m, 1H), 4.74 (dd, J=16.3, 8.4 Hz, 1H), 4.75 (d, J=12.8 Hz, 1H), 4.31 (d, J=12.8 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 133.3, 129.0, 127.9, 127.7, 127.4, 127.4, 98.5, 70.6, 67.2, 45.8; MS (EI) m/z 167, 149 (100), 71; HRMS (FAB) calculated for C12H14N3O2 (M++H) m/z 232.1086. Found: 232.1101.
