4.3. General Procedure for the Preparation of Ally Vinyl Ethers

In a two-necked 30 mL round-bottomed flask were added under an argon atmosphere 0.16 g of (E)-1,1,1-trifluoro-2,4-diphenyl-4-(prop-2-en-1-yloxy)but-2-ene 3a (0.50 mmol), 0.039 g of DBU (0.25 mmol), and THF (5.0 mL), and the whole mixture was stirred for 96 h at room temperature. After quenching the reaction by the addition of H₂O and usual workup, the crude material was purified by silica-gel chromatography using Hex:DCM = 10:1 as an eluent to furnish 0.12 g (0.36 mmol) of the title compound as a colorless oil in 73% yield.

Rf = 0.43 (Hex:DCM = 6:1). ¹H NMR: δ4.02 (1H, ddt, J = 12.8, 5.9, 1.2 Hz), 4.14 (1H, ddt, J = 12.8, 5.9, 1.2 Hz), 4.74 (1H, quint, J = 9.8 Hz), 5.15 (1H, dq, J = 10.2, 1.2 Hz), 5.21 (1H, dq, J = 17.1, 1.5 Hz), 5.57 (1H, d, J = 9.9 Hz), 5.86 (1H, ddt, J = 17.1, 10.5, 5.7 Hz), 7.25–7.47 (10H, m). ¹³C NMR: δ 46.5 (q, J = 28.5 Hz), 71.1, 107.2 (q, J = 2.5 Hz), 117.7, 126.3 (q, J = 279.1 Hz), 126.8, 127.9, 128.5, 128.6, 128.91, 128.93, 133.4, 134.9, 135.9 (q, J = 1.3 Hz), 157.2. ¹⁹F NMR: δ −70.58 (d, J = 9.3 Hz). IR (neat): ν 3033, 2931, 1654, 1495, 1251, 1165, 1111, 1052, 930, 771, 700. HRMS (FAB+, m/z): [M + H]⁺ calcd. for C₁₉H₁₈F₃O, 319.1304, found 319.1313.

Instead of (E)-1,1,1-trifluoro-2,4-diphenyl-4-{(prop-2-en-1-yl)oxy}but-2-ene 3a, 0.18 g of (E)-1,1,1-trifluoro-2-(4-methoxyphenyl)-4-phenyl-4-{(prop-2-en-1-yl)oxy}but-2-ene 3b (0.50 mmol) was employed and stirring was continued for 48 h at 40 °C to furnish 0.091 g of the title compound (0.26 mmol) was isolated in 52% yield as a colorless oil.

Rf = 0.37 (Hex:DCM = 3:1). ¹H NMR: δ 3.80 (3H, s), 4.03 (1H, ddt, J = 12.9, 5.7, 1.2 Hz), 4.14 (1H, ddt, J = 12.6, 5.7, 1.2 Hz), 4.69 (1H, quint, J = 9.6 Hz), 5.17 (1H, dq, J = 10.2, 1.2 Hz), 5.23 (1H, dq, J = 17.1, 1.5 Hz), 5.56 (1H, d, J = 9.6 Hz), 5.87 (1H, ddt, J = 17.3, 10.5, 5.7 Hz), 6.86–6.96 (2H, m), 7.30–7.40 (5H, m), 7.42–7.47 (2H, m). ¹³C NMR: δ 45.6 (q, J = 29.2 Hz), 55.1, 71.1, 107.4 (q, J = 2.5 Hz), 114.0, 117.7, 126.4 (q, J = 279.8 Hz), 126.7, 127.8 (q, J = 1.9 Hz), 128.5, 128.8, 129.9, 133.4, 134.8, 156.9, 159.2. ¹⁹F NMR: δ −71.07 (d, J = 9.0 Hz). IR (neat): ν 3061, 2934, 1613, 1514, 1251, 1163, 1110, 1036, 992, 828, 700. HRMS (FAB+, m/z): [M + H]⁺ calcd. for C₂₀H₂₀F₃O₂, 349.1410, found 349.1451.

Instead of (E)-1,1,1-trifluoro-2,4-diphenyl-4-{(prop-2-en-1-yl)oxy}but-2-ene 3a, 0.17 g of (E)-1,1,1-trifluoro-2-(4-fluorophenyl)-4-phenyl-4-{(prop-2-en-1-yl)oxy}but-2-ene 3c (0.50 mmol) was employed and stirring was continued for 96 h at room temperature to furnish 0.14 g of the title compound (0.42 mmol) was isolated in 84% yield as a colorless oil.

Rf = 0.37 (Hex:DCM = 6:1). ¹H NMR: δ 4.03 (1H, ddt, J = 12.6, 5.7, 1.5 Hz), 4.14 (1H, ddt, J = 12.6, 5.7, 1.5 Hz), 4.72 (1H, quint, J = 9.5 Hz), 5.17 (1H, dq, J = 10.8, 1.5 Hz), 5.21 (1H, dq, J = 17.1, 1.5 Hz), 5.52 (1H, d, J = 9.6 Hz), 5.85 (1H, ddt, J = 17.1, 10.2, 5.7 Hz), 7.01–7.08 (2H, m), 7.34–7.38 (5H, m), 7.39–7.46 (2H, m).¹³C NMR: δ 45.7 (q, J = 27.9 Hz), 71.0, 106.8 (q, J = 1.9 Hz), 115.5 (d, J = 21.7 Hz), 117.9, 126.2 (q, J = 279.1 Hz), 126.8, 128.5, 129.0, 130.5 (d, J = 8.1 Hz), 131.7 (q, J = 1.8 Hz), 133.2, 134.7, 157.4, 162.4 (d, J = 246.2 Hz). ¹⁹F NMR: δ −71.01 (3F, d, J = 9.0 Hz), −115.74~−115.66 (1F, m). IR (neat): ν 3084, 2935, 1655, 1607, 1512, 1251, 1167, 1112, 1052, 832, 699. HRMS (FAB+, m/z): [M]⁺ calcd. for C₁₉H₁₆F₄O, 336.1132, found 336.1164.

Instead of (E)-1,1,1-trifluoro-2,4-diphenyl-4-{(prop-2-en-1-yl)oxy}but-2-ene 3a, 0.14 g of (E)-3-(trifluoromethyl)-1-phenyl-1-{(prop-2-en-1-yl)oxy}pent-2-ene 3d (0.50 mmol) was employed and stirring was continued for 48 h with refluxing to furnish 0.08 g of the title compound (0.30 mmol) was isolated in 59% yield as a colorless oil.

Rf = 0.49 (Hex:DCM = 6:1). ¹H NMR: δ 0.98 (3H, t, J = 7.5 Hz), 1.40-1.53 (1H, m), 1.79–1.93 (1H, m), 3.34–3.51 (1H, m), 4.09–4.20 (2H, m), 4.99 (1H, d, J = 9.9 Hz), 5.21 (1H, dq, J = 10.5, 1.2 Hz), 5.27 (1H, dq, J = 17.1, 1.5 Hz), 5.95 (1H, ddt, J = 17.1, 10.5, 5.7 Hz), 7.34–7.39 (3H, m), 7.45–7.48 (2H, m). ¹³C NMR: δ11.3, 21.7, 42.0 (q, J = 26.6 Hz), 71.2, 107.7 (q, J = 2.5 Hz), 117.6, 126.7, 127.2 (q, J = 279.1 Hz), 128.5, 128.7, 133.5, 135.1, 158.1. ¹⁹F NMR: δ −71.98 (d, J = 9.3 Hz). IR (neat): ν 2972, 2880, 1659, 1323, 1254, 1173, 1121, 1068, 997, 922, 698. HRMS (FAB+, m/z): [M]⁺ calcd. for C₁₅H₁₇F₃O, 270.1226, found 270.1236.

Instead of (E)-1,1,1-trifluoro-2,4-diphenyl-4-{(prop-2-en-1-yl)oxy}but-2-ene 3a, 0.17 g of (E)-1,5-diphenyl-1-{(prop-2-en-1-yl)oxy}-3-(trifluoro-methyl)pent-2-ene 3e (0.50 mmol) was employed and stirring was continued for 24 h with refluxing to furnish 0.11 g of the title compound (0.31 mmol) was isolated in 62% yield as a colorless oil.

Rf = 0.43 (Hex:DCM = 6:1). ¹H NMR: δ1.71–1.84 (1H, m), 2.05–2.18 (1H, m), 2.57–2.80 (2H, m), 3.47–3.64 (1H, m), 4.10 (1H, ddt, J = 12.6, 5.7, 1.2 Hz), 4.17 (1H, ddt, J = 12.6, 5.4, 1.2 Hz), 5.05 (1H, d, J = 10.2 Hz), 5.17–5.29 (2H, m), 5.91 (1H, ddt, J = 17.1, 10.5, 5.7Hz), 7.16–7.22 (3H, m), 7.26–7.32 (2H, m), 7.35–7.42 (3H, m), 7.46–7.49 (2H, m). ¹³C NMR: δ 30.4 (q, J = 1.9 Hz), 32.8, 40.2 (q, J = 26.6 Hz), 71.1, 107.4 (q, J = 2.5 Hz), 117.5, 126.0, 126.8, 127.1 (q, J = 279.1 Hz), 128.39, 128.42, 128.5, 128.8, 133.5, 135.0, 141.3, 158.3. ¹⁹F NMR: δ −71.93 (d, J = 9.0 Hz). IR (neat): ν 3029, 2931, 1658, 1496, 1455, 1255, 1164, 1114, 932, 772, 698. HRMS (FAB+, m/z): [M]⁺ calcd. for C₂₁H₂₁F₃O, 346.1539, found 346.1546.

Instead of (E)-1,1,1-trifluoro-2,4-diphenyl-4-{(prop-2-en-1-yl)oxy}but-2-ene 3a, 0.19 g of (E)-1-(4-methoxyphenyl)-5-phenyl-1-{(prop-2-en-1-yl)oxy}-3-(trifluoromethyl)pent-2-ene 3f (0.50 mmol) was employed and stirring was continued for 48 h with refluxing to furnish 0.079 g of the title compound (0.21 mmol) was isolated in 42% yield as a colorless oil.

Rf = 0.40 (Hex:DCM = 6:1). ¹H NMR: δ 1.70–1.83 (1H, m), 2.06–2.18 (1H, m), 2.56–2.66 (1H, m), 3.45–3.62 (1H, m), 3.84 (3H, s), 4.09 (1H, ddt, J = 12.6, 5.4, 1.5 Hz), 4.16 (1H, ddt, J = 12.6, 5.4, 1.5 Hz), 4.95 (1H, d, J = 10.2 Hz), 5.18 (1H, dq, J = 10.5, 1.8 Hz), 5.26 (1H, dq, J = 17.4, 1.8 Hz), 5.91 (1H, ddt, J = 17.3, 10.4, 5.7 Hz), 6.89–6.93 (2H, m), 7.16–7.21 (3H, m), 7.26–7.31 (2H, m), 7.38–7.43 (2H, m). ¹³C NMR: δ 30.5 (q, J = 1.3 Hz), 32.8, 40.2 (q, J = 26.6 Hz), 55.3, 71.1, 105.9 (q, J = 2.5 Hz), 113.8, 117.4, 126.0, 127.2 (q, J = 279.1 Hz), 127.4, 128.1, 128.36, 128.42, 133.6, 141.4, 158.0, 160.1. ¹⁹F NMR: δ −72.01 (d, J = 9.0 Hz). IR (neat): ν 3030, 2954, 1608, 1511, 1291, 1253, 1111, 1034, 932, 840, 699. HRMS (FAB+, m/z): [M + H]⁺ calcd. for C₂₂H₂₄F₃O₂, 377.1723, found 377.1728.

Instead of (E)-1,1,1-trifluoro-2,4-diphenyl-4-{(prop-2-en-1-yl)oxy}but-2-ene 3a, 0.21 g of (E)-1-(4-bromophenyl)-5-phenyl-1-{(prop-2-en-1-yl)oxy}-3-(trifluoromethyl)pent-2-ene 3g (0.50 mmol) was employed and stirring was continued for 96 h at room temperature to furnish 0.21 g of the title compound (0.21 mmol) was isolated in 99% yield as a colorless oil.

Rf = 0.46 (Hex:DCM = 6:1). ¹H NMR: δ 1.71–1.84 (1H, m), 2.07–2.22 (1H, m), 2.56–2.82 (2H, m), 3.48–3.62 (1H, m), 4.07 (1H, ddt, J = 12.6, 5.4, 1.2 Hz), 4.14 (1H, ddt, J = 12.9, 5.7, 1.2 Hz), 5.05 (1H, d, J = 9.9 Hz), 5.20 (1H, dq, J = 10.2, 1.5 Hz), 5.24 (1H, dq, J = 17.1, 1.5 Hz), 5.89 (1H, ddt, J = 17.3,10.4, 5.7 Hz), 7.17–7.22 (3H, m), 7.27–7.36 (4H, m), 7.50–7.54 (2H, m). ¹³C NMR: δ 30.3 (q, J = 1.8 Hz), 32.8, 40.3 (q, J = 27.3 Hz), 71.3, 108.2 (q, J = 2.5 Hz), 117.7, 122.9, 126.1, 127.0 (q, J = 279.7 Hz), 128.3, 128.38, 128.41, 131.7, 133.2, 133.9, 141.1, 157.3. ¹⁹F NMR: δ −71.86 (d, J = 9.3 Hz). IR (neat): ν 3029, 2931, 2871, 1658, 1486, 1330, 1255, 1169, 933, 822, 699. HRMS (FAB+, m/z): [M]⁺ calcd. for C₂₁H₂₀F₃O, 424.0644, found 424.0661.