Chapter 2 Visible-Light Photoredox-Catalyzed α-Regioselective Conjugate Addition of Allyl
2.8 Supporting Information
General procedure for Acr+-Mes catalyzed reaction (milligram scale)
To a re-sealable pressure tube (13 x 100 mm) with a tiny magnetic stir bar was charged with 1 (0.6 mmol, 3.0 equiv), 2 (0.2 mmol, 1.0 equiv) and 9-mesityl-10-methylacridinium perchlorate [Acr+-Mes]
(0.82 mg, 0.002 mmol, 1.0 mol %) under argon atmosphere. Then, a mixture of degassed solvents (1 mL, 0.2 M for 2) of methanol/DCE in a ratio of 1:1 was added to that pressure tube. The resultant light greenish-yellow mixture was irradiated with 2 x 5W blue LEDs using our customized milligram scale reaction set up [Figure S 2a] under the constant stirring condition at room temperature (20-30 oC) for 24 h. After finishing the stipulated time, the solvent was removed under reduced pressure, and the residue was purified by flash column chromatography on silica gel to afford the corresponding allylated product 3.
Characterization of products:
2-(1-phenylnon-3-en-1-yl) malononitrile (3a)
Following the general procedure using 5% ethyl acetate in hexanes as eluant, 3a was obtained as a colorless liquid (40.3 mg, 77% yield, 3:1 dr); Rf = 0.20 (ethyl acetate: hexanes, 1:9); 1H NMR (300 MHz, CDCl3) δ 7.47 – 7.28 (m, 5H), 5.66 (dt, J = 14.0, 6.7 Hz, 1H), 5.26 (dt, J = 14.3, 6.9 Hz, 1H), 4.03 (d, J = 5.5 Hz, 1H), 3.23 (q, J = 7.3 Hz, 1H), 2.76 – 2.58 (m, 2H), 1.99 (q, J = 6.7 Hz, 2H), 1.38 – 1.16 (m, 6H), 0.87 (t, J = 6.8 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ 136.7, 136.6, 129.1, 128.9, 127.9, 124.2, 112.1, 111.6, 46.4, 35.5, 32.5, 31.3, 28.8, 28.7, 22.5, 14.1; FTIR (neat): υ 2920, 2250, 1720, 1600, 1500, 1450, 1380, 980, 760, 700 cm-1; HRMS m/z (EI) : calcd. For C18H22N2 (M+) 266.1783, found 266.1782. 3a- α: γ = 23:1, (E/Z: 15:1)
38 (E)-2-(1-(p-tolyl) non-3-en-1-yl) malononitrile (3b)
Following the general procedure using 5% ethyl acetate in hexanes as eluant, 3b was obtained as a colorless liquid (41.1 mg, 74% yield, Rf = 0.20 (ethyl acetate: hexanes, 1:9): 1H NMR (300 MHz, CDCl3) δ 7.22 (s, 4H), 5.74 – 5.60 (m, 1H), 5.28 (dt, J = 15.1, 7.0 Hz, 1H), 4.01 (d, J = 5.5 Hz, 1H), 3.27 – 3.15 (m, 1H), 2.77 – 2.56 (m, 2H), 2.37 (s, 3H), 1.99 (dd, J = 13.9, 6.9 Hz, 2H), 1.42 – 1.13 (m, 6H), 0.88 (t, J = 7.0 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ 138.7, 136.4, 133.7, 129.8, 127.8, 124.4, 112.2, 111.7, 46.1, 35.5, 32.5, 31.3, 28.8, 28.8, 22.5, 21.1, 14.0; FTIR (neat: υ 3040, 2960, 2920, 2860, 2280, 1740, 1720, 1530, 1480, 1470, 1390, 1380, 1200, 980, 820, 740, 520, 510 cm-1; HRMS m/z (EI) : calcd. For C19H24N2 (M+) 280.1933, found 280.1938. 3b- α: γ =24:1, (E/Z: 10:1)
(E)-2-(1-(4-(tert-butyl)phenyl) non-3-en-1-yl)malononitrile (3C)
Following the general procedure using 5% ethyl acetate in hexanes as eluant, 3c was obtained as a colorless liquid (48.9 mg, 76% yield,); Rf = 0.20 (ethyl acetate: hexanes, 1:9); 1H NMR (300 MHz, CDCl3) δ 7.40 (d, J = 10.1 Hz, 2H), 7.31 – 7.20 (d, 2H), 5.68 (dt, J = 13.9, 6.8 Hz, 1H), 5.37 – 5.21 (m, 1H), 4.03 (d, J = 5.3 Hz, 1H), 3.22 (dd, J = 12.9, 7.5 Hz, 1H), 2.76 – 2.57 (m, 2H), 2.01 (dd, J = 13.8, 6.9 Hz, 2H), 1.33 (s, 9H), 1.32 – 1.18 (m, 6H), 0.89 (t, J = 6.9 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ 151.8, 136.5, 133.6, 127.6, 126.0, 124.4, 112.3, 111.7, 45.9, 35.5, 34.6, 32.5, 31.3, 31.3, 28.8, 28.7, 22.5, 14.1; FTIR (neat) : υ 2960, 2930, 2860, 1710, 1620, 1520, 1480, 1360, 1270, 1200, 1100, 990, 830, 580 cm-1; HRMS m/z (EI) : calcd.
For C22H30N2 (M+) 322.2409, found 322.2412. 3c- α: γ = 68:1, (E/Z: 67:1)
(E)-2-(1-([1,1'-biphenyl]-4-yl)non-3-en-1-yl)malononitrile (3d)
Following the general procedure using 5% ethyl acetate in hexanes as eluant, 3d was obtained as a colorless liquid (43.7 mg, 64% yield,); Rf = 0.20 (ethyl acetate: hexanes, 1:9); 1H NMR (300 MHz, CDCl3) δ 7.69 – 7.57 (m, 4H), 7.53
39
– 7.33 (m, 5H), 5.70 (dt, J = 15.0, 6.8 Hz, 1H), 5.31 (ddd, J = 15.2, 7.7, 6.4 Hz, 1H), 4.08 (d, J = 5.4 Hz, 1H), 3.30 (td, J = 7.6, 5.5 Hz, 1H), 2.81 – 2.61 (m, 2H), 2.02 (q, J = 7.0 Hz, 2H), 1.44 – 1.15 (m, 6H), 0.88 (t, J = 7.0 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ 141.7, 140.2, 136.7, 135.6, 128.9, 128.4, 127.8, 127.6, 127.1, 124.2, 112.2, 111.6, 77.5, 77.1, 76.6, 46.1, 35.5, 32.5, 31.3, 28.8, 28.7, 22.5, 14.1;
FTIR (neat) : υ 3030, 2980, 2930, 2870, 2250, 1710, 1600, 1490, 1470, 1000, 980, 840, 760, 740, 700 cm-1 ; HRMS m/z (EI) : calcd. For C22H26N2 (M+) 342.2096, found 342.2094. 3d- α: γ; 20:1, (E/Z: 10:1)
(E)-2-(1-(4-bromophenyl)non-3-en-1-yl)malononitrile (3e)
Following the general procedure using 7% ethyl acetate in hexanes as eluant, 3e was obtained as a colorless liquid (55.0 mg, 80% yield,); Rf = 0.20 (ethyl acetate: hexanes, 1:7); 1H NMR (300 MHz, CDCl3) δ 7.58 – 7.51 (m, 2H), 7.25 – 7.18 (m, 2H), 5.66 (dtt, J = 15.1, 6.9, 1.3 Hz, 1H), 5.24 (dddd, J = 15.5, 9.5, 4.7, 3.1 Hz, 1H), 4.01 (d, J = 5.4 Hz, 1H), 3.20 (td, J = 7.7, 5.3 Hz, 1H), 2.74 – 2.52 (m, 2H), 1.98 (q, J = 7.2 Hz, 2H), 1.40 – 1.13 (m, 7H), 0.93 – 0.83 (m, 3H); 13C NMR (75 MHz, CDCl3) δ 137.0, 135.6, 132.3, 129.6, 123.8, 123.1, 111.9, 111.3, 45.8, 35.4, 32.5, 31.3, 28.8, 28.5, 22.5, 14.0; FTIR . (neat): υ 2960, 2920, 2860, 2260, 1720, 1590, 1500, 1460, 1080, 1020, 980, 840, 740, 500 cm 1; HRMS m/z (EI): calcd. For C18H21BrN2 (M+) 344.0888, found 344.0885. 3e- α: γ 24:1, (E/Z: 10:1)
(E)-2-(1-(4-chlorophenyl)non-3-en-1-yl)malononitrile (3f)
Following the general procedure using 7% ethyl acetate in hexanes as eluant, 3f was obtained as a colorless liquid (41.4 mg, 76% yield,); Rf = 0.20 (ethyl acetate: hexanes, 1:7); 1H NMR (300 MHz, CDCl3) δ 7.48 – 7.38 (m, 2H), 7.35 – 7.25 (m, 3H), 5.75 – 5.60 (m, 1H), 5.26 (ddd, J = 15.2, 7.7, 6.3 Hz, 1H), 4.04 (d, J = 5.4 Hz, 1H), 3.24 (td, J = 7.6, 5.4 Hz, 1H), 2.78 – 2.56 (m, 2H), 2.01 (q, J = 7.0 Hz, 2H), 1.43 – 1.15 (m, 6H), 0.90 (t, J = 7.0 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ 137.0, 135.1, 134.9, 129.4, 129.4, 123.8, 111.9, 111.3, 45.8, 35.4, 32.4, 31.3, 28.8, 28.6, 22.5, 14.0; FTIR(neat) : υ 3030, 2960, 2930, 2880, 2280, 1740, 1480, 1460, 1100, 980, 840, 760, 730,700 cm-1 ; HRMS m/z (EI) : calcd. For C18H21ClN2 (M+) 300.1393, found 300.1395. 3f- α: γ= 34:1, (E/Z: 20:1)
40
(E)-4-(1,1-dicyanodec-4-en-2-yl)phenyl methyl carbonate (3g)
Following the general procedure using 9% ethyl acetate in hexanes as eluant, 3g was obtained as a colorless liquid (48.9 mg, 76% yield,); Rf = 0.20 (ethyl acetate: hexanes, 1:5); 1H NMR (300 MHz, CDCl3) δ 7.38 (d, J = 8.6 Hz, 2H), 7.17 (d, J = 8.5 Hz, 2H), 5.78 – 5.62 (m, 1H), 5.29 (ddd, J = 14.8, 7.9, 6.2 Hz, 1H), 4.05 (d, J = 5.2 Hz, 1H), 3.26 (td, J = 7.6, 5.1 Hz, 1H), 2.68 (td, J = 7.5, 3.0 Hz, 2H), 2.34 (s, 3H), 2.02 (q, J = 7.1 Hz, 2H), 1.37 (dd, J = 14.7, 7.4 Hz, 2H), 1.28 (h, J = 6.6 Hz, 5H), 0.90 (t, J = 6.9 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ 169.2, 150.9, 136.9, 134.1, 129.1, 124.0, 122.3, 112.0, 111.4, 45.8, 35.5, 32.5, 31.3, 28.8, 28.6, 22.5, 21.2, 14.0 ; FTIR (neat) : υ 2970 2930, 2870, 2270, 1760, 1500, 1440, 1380, 1200, 1180, 1300, 990, 910, 870, 540 cm-1; HRMS m/z (EI) : calcd. For C20H24N2O2 (M+) 324.1838, found 324.1835.
3g- α: γ = 21:1, (E/Z: 12:1)
Methyl (E)-4-(1,1-dicyanodec-4-en-2-yl)benzoate (3h)
Following the general procedure using 5% ethyl acetate in hexanes as eluant, 3h was obtained as a colorless liquid (54.4 mg, 84% yield,); Rf = 0.20 (ethyl acetate: hexanes, 1:9); 1H NMR (300 MHz, CDCl3) δ 8.14 – 8.07 (m, 2H), 7.47 – 7.41 (m, 2H), 5.68 (dt, J = 14.9, 6.8 Hz, 1H), 5.26 (ddd, J = 15.2, 7.8, 6.4 Hz, 1H), 4.09 (d, J = 5.6 Hz, 1H), 3.95 (s, 3H), 3.32 (td, J = 7.5, 5.8 Hz, 1H), 2.81 – 2.56 (m, 2H), 2.00 (q, J = 7.0 Hz, 2H), 1.39 – 1.13 (m, 6H), 0.88 (t, J = 7.1 Hz, 3H) ; 13C NMR (75 MHz, CDCl3) δ 166.4, 141.6, 137.1, 130.7, 130.4, 128.1, 123.7, 111.8, 111.3, 52.3, 46.2, 35.4, 32.4, 31.3, 28.8, 28.4, 22.4, 14.0 ; FTIR(neat) : υ 2960, 2910, 2860, 2250, 1700, 1600, 1440, 1380, 1180, 1120, 1100, 980, 880, 790, 730, 700 cm-1 ; HRMS m/z (EI) : calcd. For C20H24N2O2 (M+) 324.1838, found 324.1835. 3h- α: γ =19:1, (E/Z: 11:1)
41 (E)-2-(1-(4-fluorophenyl)non-3-en-1-yl)malononitrile (3i)
Following the general procedure using 7% ethyl acetate in hexanes as eluant, 3i was obtained as a colorless liquid (29.9 mg, 53% yield,); Rf = 0.20 (ethyl acetate:
hexanes, 1:7); 1H NMR (300 MHz, CDCl3) δ 7.35 (dd, J = 8.6, 5.2 Hz, 2H), 7.13 (dd, J = 8.6 Hz, 2H), 5.75 – 5.61 (m, 1H), 5.36 – 5.20 (m, 1H), 4.04 (d, J = 5.3 Hz, 1H), 3.25 (dd, J = 13.0, 7.6 Hz, 1H), 2.78 – 2.57 (m, 2H), 2.01 (q, J = 7.0 Hz, 2H), 1.41 – 1.16 (m, 6H), 0.90 (t, J = 7.0 Hz, 3H) ; 13C NMR (75 MHz, CDCl3) δ 136.86, 129.71, 123.98, 116.31, 116.02,111.98, 111.34, 77.44, 77.02, 76.59, 45.68, 35.56, 32.44, 31.26, 28.79, 22.45, 14.02 ; FTIR(neat) : υ 2960, 2930, 2860, 2280, 1740, 1600, 1500, 1480, 1240, 1160, 980, 840 cm-1; HRMS m/z (EI) : calcd. For C18H21FN2 (M+) 284.1689, found 284.1689.3i- α: γ =15:1, (E/Z: 11:1)
(E)-2-(1-(2-methoxyphenyl)non-3-en-1-yl)malononitrile (3j)
Following the general procedure using 5% ethyl acetate in hexanes as eluant, 3j was obtained as a colorless liquid (34.0 mg, 43% yield,); Rf
= 0.20 (ethyl acetate: hexanes, 1:9); 1H NMR (300 MHz, CDCl3) δ 7.39 – 7.32 (m, 1H), 7.29 (dd, J = 7.6, 1.5 Hz, 1H), 7.07 – 6.92 (m, 2H), 5.70 – 5.56 (m, 1H), 5.33 – 5.21 (m, 1H), 4.22 (d, J = 6.2 Hz, 1H), 3.89 (s, 3H), 3.75 (dd, J = 14.3, 7.3 Hz, 1H), 2.72 (t, J = 7.3 Hz, 2H), 1.97 (dd, J = 13.9, 6.9 Hz, 2H), 1.37 – 1.15 (m, 6H), 0.88 (t, J = 7.0 Hz, 3H) ; 13C NMR (75 MHz, CDCl3) δ 156.9, 135.6, 129.7, 128.7, 124.8, 124.6, 121.0, 112.5, 112.2, 110.9, 55.4, 40.2, 33.8, 32.4, 31.2, 28.8, 27.4, 22.5, 14.0 ; FTIR(neat) : υ2960, 2920, 2850, 22580, 2200, 1720, 1600, 1580, 1500, 1460, 1440, 1280, 1240, 1160, 1100, 1020, 980, 850, 750, 720 cm-1; HRMS m/z (EI) : calcd. For C19H24N2O (M+) 296.1889, found 296.1890. 3j- α: γ = 22:1, (E/Z: 11:1)
(E)-2-(1-(3-methoxyphenyl)non-3-en-1-yl)malononitrile (3k)
Following the general procedure using 5% ethyl acetate in hexanes as eluant, 3k was obtained as a colorless liquid (49.1 mg, 83% yield,); Rf = 0.20 (ethyl acetate: hexanes, 1:9); 1H NMR (300 MHz, CDCl3) δ 7.35 (t,
42
J = 7.9 Hz, 1H), 6.99 – 6.84 (m, 3H), 5.77 – 5.56 (m, 1H), 5.34 – 5.22 (m, 1H), 4.04 (d, J = 5.6 Hz, 1H), 3.85 (s, 3H), 3.28 – 3.17 (m, 1H), 2.68 (t, J = 5.7 Hz, 2H), 2.01 (q, J = 6.8 Hz, 2H), 1.44 – 1.13 (m, 6H), 0.90 (t, J = 6.9 Hz, 3H) ; 13C NMR (75 MHz, CDCl3) δ 160.0, 138.2, 136.6, 130.2, 124.2, 120.1, 114.1, 113.8, 112.1, 111.6, 55.3, 46.4, 35.5, 32.5, 31.3, 28.8, 28.6, 22.5, 14.0 ; FTIR(neat) : υ 3060, 3030, 2940, 2860, 2260, 1720, 1600, 1480, 1460, 1380, 1260, 1100, 980, 760, 700 cm-1 ; HRMS m/z (EI) : calcd. For C19H24N2O (M+) 3296.1889, found 296.1891. 3k- α: γ =36:1, (E/Z: 10:1)
(E)-2-(1-(4-methoxyphenyl)non-3-en-1-yl)malononitrile (3l)
Following the general procedure using 5% ethyl acetate in hexanes as eluant, 3l was obtained as a colorless liquid (23.6 mg, 40% yield,); Rf = 0.20 (ethyl acetate: hexanes, 1:9); Following the general procedures, 3l were obtained as a colourless liquid in the yield of 40 % (23.6 mg); 1H NMR (300 MHz, CDCl3) δ 7.28 (dd, J = 5.8, 3.0 Hz, 2H), 6.99 – 6.92 (m, 2H), 5.75 – 5.57 (m, 1H), 5.28 (ddd, J = 15.2, 7.8, 6.3 Hz, 1H), 4.02 (d, J = 5.3 Hz, 1H), 3.84 (s, 3H), 3.21 (td, J = 7.6, 5.4 Hz, 1H), 2.78 – 2.53 (m, 2H), 2.01 (q, J = 6.9 Hz, 2H), 1.44 – 1.13 (m, 6H), 0.90 (t, J = 6.9 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ 159.8, 136.4, 129.1, 128.6, 124.4, 114.5, 112.3, 111.6, 55.3, 45.7, 35.6, 32.5, 31.3, 29.0, 28.8, 22.5, 14.0; FTIR (neat): υ 2950, 2930, 2860, 2250, 1620, 1520m 1470, 1300, 1250, 1180, 1120, 980, 830 cm-1; HRMS m/z (EI) : calcd.
For C19H24N2O (M+) 296.1889, found 296.1891. 3l- α: γ =17:1, (E/Z: 12:1)
(E)-4-(1,1-dicyanodec-4-en-2-yl)-2-methoxyphenyl acetate (3m)
Following the general procedure using 10 % ethyl acetate in hexanes as eluant, 3m was obtained as a colorless liquid (45.9 mg, 64% yield,); Rf = 0.20 (ethyl acetate: hexanes, 1:5); 1H NMR (300 MHz, CDCl3) δ 7.07 (d, J
= 8.0 Hz, 1H), 6.97 – 6.88 (m, 2H), 5.69 (dt, J = 13.8, 6.8 Hz, 1H), 5.28 (dt, J = 14.2, 7.0 Hz, 1H), 4.04 (d, J = 4.9 Hz, 1H), 3.85 (s, 3H), 3.26 – 3.14 (m, 1H), 2.66 (t, J = 7.3 Hz, 2H), 2.32 (s, 3H), 2.00 (dd, J
= 13.7, 6.9 Hz, 2H), 1.30 (ddd, J = 17.9, 12.9, 8.5 Hz, 6H), 0.88 (t, J = 6.8 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ 168.8, 151.5, 140.1, 136.9, 135.5, 124.1, 123.4, 120.2, 112.0, 111.5, 56.0, 46.2, 35.5, 32.5,
43
31.3, 28.8, 28.6, 22.5, 20.7, 14.0; FTIR(neat) : υ 3010, 2960, 2930, 2850, 2250, 1760, 1710, 1600, 1500, 1460, 1420, 1370, 1270, 1200, 1160, 1150, 1030, 980, 900, 890, 820, 730, 660, 600, 530 cm-1; HRMS m/z (EI) : calcd. For C21H26N2O3 (M+) 354.1943, found 354.1944.
3m- α: γ =, (E/Z: 10:1)
(E)-2-(1-(4-(benzyloxy)-3,5-dimethylphenyl)non-3-en-1-yl)malononitrile (3n)
Following the general procedure using 10 % ethyl acetate in hexanes as eluant, 3n was obtained as a colorless liquid (36.0 mg, 45% yield,); Rf = 0.20 (ethyl acetate: hexanes, 1:5); 1H NMR (300 MHz, CDCl3) δ 7.50 – 7.32 (m, 5H), 6.98 (s, 2H), 5.66 (dt, J = 13.9, 6.8 Hz, 1H), 5.26 (dt, J = 8.0, 6.3 Hz, 1H), 4.83 (s, 2H), 3.99 (d, J
= 5.5 Hz, 1H), 3.13 (dd, J = 13.1, 7.6 Hz, 1H), 2.63 (dd, J = 12.2, 7.0 Hz, 2H), 2.31 (s, J = 8.1 Hz, 6H), 2.00 (dd, J = 13.9, 6.8 Hz, 2H), 1.40 – 1.13 (m, 6H), 0.88 (t, J = 6.9 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ 156.0, 137.4, 136.4, 128.5, 128.3, 128.0, 127.7, 124.4, 112.2, 111.7, 74.0, 45.8, 35.7, 32.5, 31.3, 28.9, 28.8, 22.5, 16.6, 14.1; FTIR(neat) : υ 2920, 2890, 1725, 1565, 1500, 1460, 1380, 1360, 1200; HRMS m/z (EI) : calcd. For C27H32N2O (M+) 400.2515, found 400.2516.
3n- α: γ =53:1, (E/Z: 42:1)
(E)-2-(undec-5-en-3-yl) malononitrile (3o)
Following the general procedure using 5% ethyl acetate in hexanes as eluant, 3o was obtained as a colorless liquid (43.6 mg, 71%
yield,); Rf = 0.20 (ethyl acetate: hexanes, 1:9); 1H NMR (300 MHz, CDCl3) δ 5.66 (dt, J = 14.9, 6.7 Hz, 1H), 5.39 – 5.23 (m, 1H), 3.84 (d, J = 4.7 Hz, 1H), 2.41 (ddd, J = 11.4, 9.0, 3.1 Hz, 1H), 2.24 – 1.92 (m, 4H), 1.85 – 1.71 (m, 1H), 1.67 – 1.54 (m, 1H), 1.45 – 1.21 (m, 6H), 1.08 (td, J = 7.4, 4.1 Hz, 3H), 0.92 (t, J = 6.9 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ 136.6, 124.2, 112.6, 111.8, 42.0, 33.8, 32.5, 31.4, 28.9, 26.4, 24.2, 14.1, 11.2; FTIR(neat) : υ 2980, 2920, 2860, 2280, 1740, 1580, 1470, 1380, 1200, 980, 540 cm-1; HRMS m/z (EI) : calcd. For C14H22N2 (M+) 218.1783, found 217.1784.3o- α: γ =1:0, (E/Z: 13:1).
44 (E)-2-(2-methylundec-5-en-3-yl)malononitrile (3p)
Following the general procedure using 5% ethyl acetate in hexanes as eluant, 3p was obtained as a colorless liquid (32.0 mg, 69 % yield,); Rf = 0.20 (ethyl acetate: hexanes, 1:9); Following the general procedures, 3p were obtained as a colourless liquid in the yield of 69 % (32.0 mg). Rf = 0.20 ( EtOAc : Hexane, 1:9); 1H NMR (300 MHz, CDCl3) δ 5.82 – 5.61 (m, 1H), 5.35 (ddd, J = 9.2, 4.9, 3.6 Hz, 1H), 3.92 (d, J = 4.1 Hz, 1H), 2.57 – 2.40 (m, 1H), 2.28 – 1.99 (m, 4H), 1.97 – 1.83 (m, 1H), 1.47 – 1.22 (m, 6H), 1.17 – 1.03 (m, 6H), 0.91 (t, J = 6.8 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ 136.5, 125.0, 112.8, 112.4, 46.2, 32.5, 31.9, 31.4, 29.9, 28.8, 24.6, 22.5, 20.8, 19.0; FTIR (neat) : υ 2960, 2920, 2880, 2850, 2250, 1740, 1640, 1440, 1390, 1380, 1220, 980 cm-1; HRMS m/z (EI) : calcd. For C15H24N2
(M+) 232.1939, found 231.1941. 3p- α: γ = 1:0, (E/Z: 15:1)
(E)-2-(1-cyclohexylnon-3-en-1-yl) malononitrile (3q)
Following the general procedure using 5% ethyl acetate in hexanes as eluant, 3q was obtained as a colorless liquid (32.7 mg, 76% yield,); Rf = 0.20 (ethyl acetate: hexanes, 1:9); 1H NMR (300 MHz, CDCl3) δ 5.78 – 5.61 (m, 1H), 5.44 – 5.24 (m, 1H), 3.93 (d, J = 4.0 Hz, 1H), 2.48 (dt, J = 13.3, 4.7 Hz, 1H), 2.20 (dt, J
= 14.7, 8.9 Hz, 1H), 2.13 – 1.99 (m, 2H), 1.95 – 1.62 (m, 6H), 1.48 – 1.05 (m, 12H), 0.91 (t, J = 6.8 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ 136.5, 125.1, 112.5, 45.7, 39.7, 32.5, 32.3, 31.4, 31.0, 29.6, 28.8, 26.3, 26.1, 26.1, 24.4, 22.5, 14.1; FTIR (neat): υ 2920, 28850, 2250, 1740, 1640, 1450, 1220, 980 cm-
1; HRMS m/z (EI) : calcd. For C18H28N2 (M+) 272.2252, found 272.2250. 3q- α: γ = 44:1, (E/Z: 13:1)
(E)-2-(tetradec-8-en-6-yl) malononitrile (3r)
Following the general procedure using 5% ethyl acetate in hexanes as eluant, 3r was obtained as a colorless liquid (32.7 mg, 63 % yield,); Rf = 0.20 (ethyl acetate: hexanes,
45
1:9); 1H NMR (300 MHz, CDCl3) δ 5.66 (dt, J = 14.1, 6.8 Hz, 1H), 5.30 (dt, J = 14.7, 7.0 Hz, 1H), 3.84 (d, J = 4.6 Hz, 1H), 2.41 (dt, J = 11.8, 5.5 Hz, 1H), 2.21 – 1.95 (m, 4H), 1.72 – 1.28 (m, 14H), 1.04 – 0.81 (m, 6H); 13C NMR (75 MHz, CDCl3) δ 136.6, 124.2, 112.6, 111.8, 40.5, 34.3, 32.5, 31.5, 31.4, 31.1, 28.9, 26.6, 26.3, 22.5, 22.4, 14.1, 14.0; FTIR (neat): υ 2960, 2930, 2860, 2280, 1760, 1550, 1470, 1380, 980, 720 cm-1; HRMS m/z (EI) : calcd. For C17H28N2 (M+) 260.2252, found 259.2178. 3r- α: γ = 1:0, (E/Z: 15:1)
2-(3-methyl-1-phenylbut-3-en-1-yl)malononitrile (3t)
Following the general procedure using 5% ethyl acetate in hexanes as eluant, 3t was obtained as a colorless liquid (36.1 mg, 86% yield,); Rf = 0.20 (ethyl acetate: hexanes, 1:9); 1H NMR (300 MHz, CDCl3) δ 7.51 – 7.36 (m, 5H), 4.94 (dd, J = 8.8, 7.4 Hz, 2H), 4.05 (d, J = 4.9 Hz, 1H), 3.50 – 3.30 (m, 1H), 2.83 (dd, J = 14.1, 8.8 Hz, 1H), 2.64 (dd, J = 14.2, 7.0 Hz, 1H), 1.77 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 140.4, 136.5, 129.2, 129.0, 128.0, 115.5, 112.1, 111.4, 44.1, 40.3, 29.0, 22.0; FTIR(neat) : υ 3060, 3030, 2920, 2260, 1740, 1700, 1600, 1260, 940, 840, 760, 700 cm-1; HRMS m/z (EI) : calcd. For C14H14N2 (M+) 210.1157 found 210.1158.
(E)-2-(4-cyclohexyl-1-phenylbut-3-en-1-yl)malononitrile (3u)
Following the general procedure using 5% ethyl acetate in hexanes as eluant, 3u was obtained as a colorless liquid (48.3 mg, 87% yield,); Rf = 0.20 (ethyl acetate: hexanes, 1:9); 1H NMR (300 MHz, CDCl3) δ 7.51 – 7.38 (m, 3H), 7.38 – 7.32 (m, 2H), 5.64 (dd, J = 15.4, 6.8 Hz, 1H), 5.34 – 5.18 (m, 1H), 4.05 (d, J = 5.5 Hz, 1H), 3.25 (td, J = 7.5, 5.7 Hz, 1H), 2.78 – 2.56 (m, 2H), 1.93 (dt, J = 14.3, 5.5 Hz, 1H), 1.69 (ddd, J = 27.6, 10.9, 7.9 Hz, 5H), 1.35 – 1.16 (m, 3H), 1.15 – 0.94 (m, 2H); 13C NMR (75 MHz, CDCl3) δ 142.4, 136.8, 129.1, 128.8, 127.9, 121.7, 112.2, 111.6, 46.4, 40.6, 35.6, 32.8, 32.7, 28.6, 26.1, 25.9, 25.9; FTIR (neat):
υ 3900, 3500, 2900, 2260, 1720, 16660, 1500, 1460, 1360, 1260, 1240, 1110, 900, 870, 760, 700, 540 cm-1; HRMS m/z (EI) : calcd. For C19H22N2 (M+) 278.1783, found 278.1780. 3u- α: γ =1:0, (E/Z: 13:1)
46 (E)-2-(1,5-diphenylpent-3-en-1-yl)malononitrile (3v)
Following the general procedure using 5% ethyl acetate in hexanes as eluant, 3v was obtained as a colorless liquid (40.0 mg, 70 % yield,); Rf = 0.20 (ethyl acetate: hexanes, 1:9); 1H NMR (300 MHz, CDCl3) δ 7.60 – 7.39 (m, 4H), 7.38 – 7.29 (m, 3H), 7.28 – 7.17 (m, 2H), 7.08 – 7.05 (m, 1H), 5.82 (tt, J = 15.8, 7.9 Hz, 1H), 5.34 (dtd, J = 10.4, 6.5, 1.4 Hz, 1H), 4.01 (d, J = 5.7 Hz, 1H), 3.34 (d, J = 7.1 Hz, 2H), 3.29 (dt, J = 7.6, 3.8 Hz, 1H), 2.86 – 2.64 (m, 2H); 13C NMR (75 MHz, CDCl3) δ 139.7, 136.5, 134.7, 129.2, 128.9, 128.5, 128.4, 127.9, 126.2, 125.9, 112.0, 111.6, 46.3, 38.8, 35.4, 28.9; FTIR(neat) : υ 3070, 3030, 2920, 2310, 1740, 1600, 1510, 1440, 960, 740, 700 cm-1;HRMS m/z (EI) : calcd. For C20H18N2 (M+) 286.1470, found 286.1466. 3v- α: γ = 1:0, (E/Z: 13:1)
(E)-2-(6-(benzyloxy)-1-phenylhex-3-en-1-yl)malononitrile (3w)
Following the general procedure using 5% ethyl acetate in hexanes as eluant, 3w was obtained as a colorless liquid (46.7 mg, 71% yield,); Rf = 0.20 (ethyl acetate: hexanes, 1:9); 1H NMR (300 MHz, CDCl3) δ 7.47 – 7.29 (m, 10H), 5.73 (dt, J = 13.8, 6.8 Hz, 1H), 5.45 – 5.30 (m, 1H), 4.52 (s, 2H), 4.09 (d, J = 5.6 Hz, 1H), 3.52 (t, J = 6.3 Hz, 2H), 3.28 – 3.16 (m, 1H), 2.76 – 2.65 (m, 2H), 2.35 (q, J = 6.4 Hz, 2H); 13C NMR (75 MHz, CDCl3) δ 138.2, 136.7, 132.9, 129.1, 128.9, 128.5, 127.9, 127.8, 127.8, 126.5, 112.2, 111.6, 73.1, 69.3, 46.1, 35.5, 33.0, 28.4; FTIR (neat): υ 3300, 3000, 2900, 2800, 2260, 1700, 1600, 1500, 1460, 1360, 1220, 1100, 980, 740, 700 cm-1; HRMS m/z (EI) : calcd. For C22H22N2O (M+) 330.1732, found 330.1730. 3w - α: γ =74:1, (E/Z: 17:1)
(E)-2-(8-(benzyloxy)-1-phenyloct-3-en-1-yl)malononitrile (3x)
Following the general procedure using 5% ethyl acetate in hexanes as eluant, 3x was obtained as a colorless liquid (54.4 mg, 76% yield,);
Rf = 0.20 (ethyl acetate: hexanes, 1:9); 1H NMR (300 MHz, CDCl3) δ 7.44 – 7.31 (m, 10H), 5.75 – 5.59 (m, 1H), 5.40 – 5.22 (m, 1H), 4.52 (s, 2H), 4.04 (d, J = 5.5 Hz, 1H),
47
3.46 (t, J = 6.3 Hz, 2H), 3.28 – 3.16 (m, 1H), 2.77 – 2.58 (m, 2H), 2.04 (q, J = 7.1 Hz, 2H), 1.68 – 1.53 (m, 2H), 1.53 – 1.38 (m, 2H); 13C NMR (75 MHz, CDCl3) δ 138.6, 136.7, 136.1, 129.2, 128.9, 128.4, 127.9, 127.7, 127.6, 124.6, 112.1, 111.6, 72.9, 70.1, 53.5, 46.3, 35.5, 32.2, 29.1, 28.7, 25.8; FTIR (neat):
υ 3070, 3020, 2940, 2890, 2260,1700, 1600, 1500, 1480, 1360, 1200, 1100, 980, 760, 700 cm-1; HRMS m/z (EI) : calcd. For C24H26N2O (M+) 358.2045, found 358.2047.3x - α: γ = 27:1, (E/Z: 8:1)
Synthetic application of synthesized ether products Gram-scale reaction
An oven-dried 100 mL round bottomed flask containing a magnetic stir bar was charged with 1c (2.49 g, 3.0 equiv), 2a (1.00g, 1.0 equiv) and catalyst MesAcr-+ClO4- (26.7 mg, 1.0 mol %) under argon atmosphere. Then, a mixture of degassed solvents (50 mL, 0.2 M for 2a) of dichloromethane/methanol in a ratio of 1:1 was added to that round bottomed flask. The resultant mixture was irradiating with Kessil 40W blue LEDs under constant stirring condition at room temperature for 72 h as shown in [Figure S 2b]. After finishing the stipulated time, the solvent was removed under reduced pressure and residue was purified by flash column chromatography on silica gel to afford the corresponding product 3t (954 mg, 70%)
Product Diversification
Scheme 2.6
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In an oven dried reaction tube, Cs2CO3 (2.0 equiv, 0.40 mmol,130 mg) degassed CH3CN (0.4 mL, 0.5 M) was added then, 3t (1.0 equiv., 0.2 mmol), and then the benzyl alcohol (5.0 equiv., 1 mmol, 108 mg) were added Scheme 2.6. The reaction was heated at 60 °C in O2 atmosphere until TLC indicated all the malononitrile had disappeared; after which, the reaction was filtered through a short silica column and washed with CHCl3 (25 mL ×3), then concentrated and the residue was purified by silica gel column chromatography with 5% ethyl acetate in hexanes as eluent. Ester 4a was obtained as a colorless liquid in the yield of 65% (36 mg). Rf= 0.3 (Ethyl acetate; hexanes 1:8), 1H NMR (300 MHz, CDCl3) δ 7.38 – 7.30 (m, 7H), 7.28 – 7.22 (m, 3H), 5.21 – 5.02 (m, 2H), 4.73 (dt, J = 12.8, 1.3 Hz, 2H), 3.89 (dd, J = 9.2, 6.4 Hz, 1H), 2.89 (dd, J = 14.7, 9.2 Hz, 1H), 2.48 (dd, J = 14.7, 6.3 Hz, 1H), 1.74 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 173.4, 142.6, 138.7, 135.9, 128.6, 128.4, 128.1, 128.0, 128.0, 127.3, 112.2, 66.5, 50.1, 41.3, 30.9, 22.6.
Scheme 2.7
At – 20 oC, m-CPBA (51.7 mg, 0.3 mmol, 1.5 equiv) was added to a 3t (42 mg, 0.2 mmol, 1.0 equiv) and Cs2CO3 (65 mg, 0.2 mmol, 1.05 equiv) in MeOH (1.0 mL). After 12 hrs, the reaction was warmed to room temperature and stirred for another 12 hrs Scheme 2.7. The mixture was filtered through a short column of SiO2 and purified by silica gel column chromatography with 5% ethyl acetate in hexanes as eluent. Ester 4b was obtained as colorless liquid in the yield of 70% (26 mg). Rf = 0.3 (ethyl acetate:
hexanes, 1:8); 1H NMR (300 MHz, CDCl3) δ 7.38 – 7.29 (m, 5H), 4.77 (t, J = 1.6 Hz, 1H), 4.71 (dq, J
= 2.0, 1.1 Hz, 1H), 3.84 (dd, J = 9.1, 6.4 Hz, 1H), 3.68 (s, 3H), 2.87 (dd, J = 14.6, 9.3 Hz, 1H), 2.52 – 2.39 (m, 1H), 1.75 (t, J = 1.1 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ 174.1, 142.7, 138.8, 128.6, 127.9, 127.3, 112.1, 52.0, 50.0, 41.3, 22.6.
49