Reaction Steps
According to the general procedure for homologation, methoxymethyl triphenylphosphonium chloride (1.09 g, 3.18 mmol) in dry THF (4 mL), NaOtBu (0.382 g, 3.9 mmol), ketone 13 (0.400 g, 1.59 mmol) in THF (3 mL) were stirred at 0° C. Following the general workup, the mixture of enol ethers (0.330 g, 1.18 mmol) in THF/H2O (9:1, 5 mL) were hydrolyzed using Hg(OAc)2 (1.13 g, 3.5 mmol) at room temperature. After the general extraction procedure, aldehyde (0.285 g, 1.1 mmol) in MeOH (3 mL), Ohira-Bestmann reagent (0.442 g, 2.15 mmol) dissolved in MeOH (1 mL), powdered K2CO3 (0.370 g, 2.68 mmol) were stirred at 0° C. Following the general workup and flash chromatography (SiO2, 10 g, 5% EtOAc/hexanes) alkyne 22 was obtained as a white solid (0.200 g, 47% yield over 3 steps); TLC Rf=0.2 (5% EtOAc/hexanes); mp 103.7-104° C.; 1H NMR (500 MHz, CDCl3) δ 7.72 (m, 2H), 7.67 (m, 3H), 7.19 (d, J=7.9 Hz, 1H), 7.03 (s, 1H), 4.23 (q, J=7.0, 1H), 3.92 (s, 3H), 2.25 (d, J=2.4 Hz, 1H), 1.48 (d, J=7.0 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 156.7, 145.8, 139.3, 132.7, 131.9. 128.6, 127.9, 119.9, 119.9, 119.1, 111.1, 109.5, 87.3, 69.9, 55.8, 25.4, 22.8; IR (neat cm−1) 3285, 3069, 2935, 2221, 1604, 1488, 1393, 1225, 1024, 807, 657; HRMS (DART, M++H) m/z 262.1253 (calculated for C18H16NO, 262.1232).
