Full experimental details can be found in the Supporting Information .
To a solution of (S,S)-ProPhenol ligand (20.8 mg, 0.0325 mmol, 10 mol%), triphenylphosphine oxide (18 mg, 0.065 mmol, 20 mol %) and TMS-acetylene (56 μL, 0.39 mmol, 1.2 equiv) in anhydrous toluene (0.44 mL) was added dimethyl zinc (406 μL, 1.2 M solution in toluene, 0.488 mmol, 1.5 equiv) at 0 °C (0.813 mL total toluene, 0.48 M alkyne concentration). The reaction was warmed to room temperature and stirred for 60 minutes before addition of the trans-cinammaldehyde (43 mg, 0.325 mmol, 1 equiv) at 0 °C. The reaction was stirred for 48 hours at 4 °C before quenching with saturated, aqueous NH4Cl. The organic phase was extracted three times with Et2O and the combined organics were concentrated in vacuo. The crude product was purified by flash column chromatography. The title compound was isolated as a white solid (67 mg, 83% yield). Melting Point: 57-58 °C. [α]D25 = +2.16° (c = 1.05, CHCl3). 1H-NMR (400 MHz, CDCl3): δ 7.40-7.43 (m, 2H), 7.32-7.36 (m, 2H), 7.25-7.29 (m, 1H), 6.77 (dd, J = 16, 1.2 Hz, 1H), 6.29 (dd, J = 16, 6 Hz, 1H), 5.05 (dt, J = 6, 1.2 Hz, 1H), 1.96 (t, J = 6 Hz, 1H), 0.21 (s, 9H). 13C-NMR (101 MHz, CDCl3): δ 136.0, 132.0, 128.6, 128.1, 127.8, 126.8, 104.1, 91.3, 66.3, −0.2. IR (film): 3300 (br, OH), 2960, 2172, 1654, 1496, 1449, 1407, 1251 cm−1. HRMS–EI (m/z): calculated for C14H18OSi: 230.1127, found: 230.1126, 0.6 ppm. Chiral HPLC: Chiralcel® AD column, heptane/iPrOH = 90/10, 1.0 mL/min, λ = 254 nm: 6.97/8.79 min (88% ee). Characterization data matches literature.[45 ]![]()
To a solution of (S,S)-ProPhenol ligand (20.8 mg, 0.0325 mmol, 10 mol%), triphenylphosphine oxide (18 mg, 0.065 mmol, 20 mol %) and TMS-acetylene (56 μL, 0.39 mmol, 1.2 equiv) in anhydrous toluene (0.44 mL) was added dimethyl zinc (406 μL, 1.2 M solution in toluene, 0.488 mmol, 1.5 equiv) at 0 °C (0.813 mL total toluene, 0.48 M alkyne concentration). The reaction was warmed to room temperature and stirred for 60 minutes before addition of the trans-cinammaldehyde (43 mg, 0.325 mmol, 1 equiv) at 0 °C. The reaction was stirred for 48 hours at 4 °C before quenching with saturated, aqueous NH4Cl. The organic phase was extracted three times with Et2O and the combined organics were concentrated in vacuo. The crude product was purified by flash column chromatography. The title compound was isolated as a white solid (67 mg, 83% yield). Melting Point: 57-58 °C. [α]D25 = +2.16° (c = 1.05, CHCl3). 1H-NMR (400 MHz, CDCl3): δ 7.40-7.43 (m, 2H), 7.32-7.36 (m, 2H), 7.25-7.29 (m, 1H), 6.77 (dd, J = 16, 1.2 Hz, 1H), 6.29 (dd, J = 16, 6 Hz, 1H), 5.05 (dt, J = 6, 1.2 Hz, 1H), 1.96 (t, J = 6 Hz, 1H), 0.21 (s, 9H). 13C-NMR (101 MHz, CDCl3): δ 136.0, 132.0, 128.6, 128.1, 127.8, 126.8, 104.1, 91.3, 66.3, −0.2. IR (film): 3300 (br, OH), 2960, 2172, 1654, 1496, 1449, 1407, 1251 cm−1. HRMS–EI (m/z): calculated for C14H18OSi: 230.1127, found: 230.1126, 0.6 ppm. Chiral HPLC: Chiralcel® AD column, heptane/iPrOH = 90/10, 1.0 mL/min, λ = 254 nm: 6.97/8.79 min (88% ee). Characterization data matches literature.[45 ]