반응 단계
The product was prepared by General procedure T using 98 mg (0.55 mmol) Cy2BH, 68 μL (0.55 mmol) 3,3-dimethyl-1-butyne, 0.78 mL (1.55 mmol, 2.0 M in hexanes) Et2Zn, 4.8 mg (0.02 mmol) (−)-MIB, 54 μL (0.50 mmol) p-fluorobenzaldehyde, 100 μL (0.10 mmol, 1.0 M in hexanes) Ti(OiPr)4, and 21 μL (0.10 mmol) (+)-DIPT. The crude product was purified by column chromatography (5% ethyl acetate in hexanes) to afford the title compound in 92% yield (103 mg, 0.46 mmol). threo-diastereomer: Colorless solid. m.p.: 83-85° C.; [α]D20=−14.8 (c=0.23, CHCl3); 1H NMR (CDCl3, 500 MHz): δ 0.82 (s, 9H), 2.31 (br s, 1H), 2.78 (d, 1H, J=2.1 Hz), 2.95 (dd, 1H, J=5.5, 2.2 Hz), 4.42 (d, 1H, J=5.2 Hz), 6.99 (t, 2H, J=8.6 Hz), and 7.31 (dd, 2H, J=8.3, 5.5 Hz) ppm; 13C{1H} NMR (CDCl3, 125 MHz): δ 25.7, 30.6, 59.2, 65.1, 73.6, 115.4, 115.6, 127.68, 127.74, 136.2, and 163.5 ppm; IR (neat): 3403, 3002, 2963, 2919, 2872, 1725, 1661, 1637, 1603, 1511, 1461, 1390, 1361, and 1226 cm−1; HRMS-CI m/z 224.1206 [M+; calcd for C13H17FO2: 224.1213]. erythro-diastereomer: Colorless solid. m.p.: 56-59° C.; [α]D20=−34.3 (c=0.40, CHCl3); 1H NMR (CDCl3, 500 MHz): δ 0.85 (s, 9H), 2.28 (br s, 1H), 2.96 (d, 1H, J=2.1 Hz), 3.01 (t, 1H, J=2.7 Hz), 4.84 (br d, 1H, J=2.8 Hz), 7.04 (t, 2H, J=8.5 Hz), and 7.34 (dd, 2H, J=8.3, 5.5 Hz) ppm; 13C{1H} NMR (CDCl3, 125 MHz): δ 25.8, 30.4, 58.2, 62.7, 70.5, 115.4, 115.6, 128.08, 128.15, 135.6, and 163.6 ppm; IR (KBr): 3409, 3015, 2964, 2871, 1606, 1510, 1463, 1392, 1369, 1331, and 1316 cm−1; HRMS-CI m/z 224.1206 [M+; calcd for C13H17FO2: 224.1213].
