Organic & Biomolecular Chemistry
Paper
6.01–6.10 (m, 1H), 5.64 (br s, 1H), 5.01–5.08 (m, 2H), 3.93 (AB, 1H), 2.81 (dd, J = 4.8, 11.4 Hz, 1H), 2.48 (dd, J = 6.9, 11.4 Hz,
JAB = 15.2 Hz, 1H), 3.84 (AB, JAB = 13.6 Hz, 1H), 3.83 (s, 3H), 1H).
3.63–3.61 (m, 1H), 3.57 (BA, JBA = 13.2 Hz, 1H), 3.20 (BA, JBA
=
2j/3j > 19/1. 2j,12 white solid, 75% yield, 91% ee. [Daicel
15.6 Hz, 1H), 2.87 (d, J = 11.2 Hz, 1H), 2.43 (dd, J = 4.0, Chiralpak IC (0.46 cm × 25 cm); n-hexane–2-propanol = 90/10;
11.2 Hz, 1H).
flow rate = 0.5 mL min−1; detection wavelength = 230 nm; tR
=
2d,12 colorless oil, 61% yield, 91% ee. [Daicel Chiralpak 8.80 (major), 8.14 (minor) min]. [α]D20 = −86.9 (c = 0.5, CHCl3).
AD-H (0.46 cm × 25 cm); n-hexane–2-propanol = 85/15; flow 1H NMR (300 MHz, CDCl3) δ 7.07 (t, J = 7.5 Hz, 1H), 6.65–6.72
rate = 0.5 mL min−1; detection wavelength = 230 nm; tR = 14.91 (m, 2H), 5.84–6.14 (m, 2H), 5.44 (br s, 1H), 5.18–5.35 (m, 4H),
(major), 18.69 (minor) min]. [α]2D0 = −63.5 (c = 0.5, CHCl3). H 3.72 (AB, JAB = 14.7 Hz, 1H), 3.55–3.63 (m, 1H), 3.48 (BA, JBA
=
1
NMR (400 MHz, CDCl3) δ 7.25–7.38 (m, 6H), 6.63 (d, J = 8.8 Hz, 15.0 Hz, 1H), 3.20 (dd, J = 6.0, 13.8 Hz, 1H), 3.08 (dd, J = 6.6,
1H), 6.00–6.10 (m, 1H), 5.31 (br s, 1H), 5.20–5.26 (m, 2H), 3.83 13.5 Hz, 1H), 2.72–2.75 (m, 2H).
(AB, JAB = 16.0 Hz, 1H), 3.81 (AB, JAB = 13.2 Hz, 1H), 3.63 (BA,
2k/3k > 19/1. 2k, white solid, mp 110–111 °C, 38% yield,
JBA = 13.6 Hz, 1H), 3.48–3.51 (m, 1H), 3.40 (BA, JBA = 16.4 Hz, 92% ee. [Daicel Chiralpak AS-H (0.46 cm × 25 cm); n-hexane–
1H), 2.75 (dd, J = 4.0, 11.2 Hz, 1H), 2.61 (dd, J = 4.4, 11.2 Hz, 2-propanol = 90/10; flow rate = 0.5 mL min−1; detection wave-
1H).
length = 254 nm; tR = 9.25 (major), 10.59 (minor) min]. [α]D20
=
2e/3e > 19/1. 2e,12 colorless oil, 30% yield, 92% ee. [Daicel −73.6 (c = 0.5, CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.28 (d, J =
Chiralpak AS-H (0.46 cm × 25 cm); n-hexane–2-propanol = 95/ 8.4 Hz, 1H), 6.61 (d, J = 8.4 Hz, 1H), 6.01–6.14 (m, 1H),
5; flow rate = 0.5 mL min−1; detection wavelength = 230 nm; 5.84–5.96 (m, 1H), 5.55 (br s, 1H), 5.19–5.31 (m, 4H), 3.76 (AB,
tR = 9.62 (major), 10.94 (minor) min]. [α]2D0 = 3.7 (c = 0.5, CHCl3). JAB = 16.4 Hz, 1H), 3.52–3.57 (m, 1H), 3.38 (BA, JBA = 16.0 Hz,
1H NMR (300 MHz, CDCl3) δ 11.13 (br s, 1H), 7.90 (d, J = 1H), 3.27 (dd, J = 6.0, 13.6 Hz, 1H), 3.12 (dd, J = 6.4, 13.6 Hz,
9.0 Hz, 1H), 7.26–7.39 (m, 5H), 6.64 (d, J = 9.0 Hz, 1H), 1H), 2.78 (dd, J = 3.6, 10.8 Hz, 1H), 2.63 (dd, J = 4.0, 11.6 Hz,
6.03–6.15 (m, 1H), 5.06–5.13 (m, 2H), 3.92 (AB, JAB = 17.1 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 151.9, 138.0, 133.1, 132.5,
1H), 3.63–3.76 (m, 3H), 3.37 (BA, JBA = 16.8 Hz, 1H), 3.01 (d, J = 129.1, 122.2, 116.1, 115.1, 113.6, 111.2, 58.6, 55.0, 53.1, 37.7;
11.4 Hz, 1H), 2.54 (dd, J = 3.9, 11.4 Hz, 1H).
IR (film): vmax/cm−1 = 2934, 2903, 2819, 2780, 1857, 1749,
2f,12 colorless oil, 93% yield, 66% ee. [Daicel Chiralpak IC 1642, 1576, 1434, 1359, 1332, 1285, 1244, 1181, 1140, 1068,
(0.46 cm × 25 cm); n-hexane–2-propanol = 80/20; flow rate = 1045, 992, 914, 811, 732, 654, 627; ESI-HRMS (m/z): exact mass
0.5 mL min−1; detection wavelength = 230 nm; tR = 16.54 calcd for C14H17BrNO [M + H]+: 294.0488. Found: 294.0494.
(major), 12.03 (minor) min]. [α]2D0 = −31.5 (c = 1.0, CHCl3). H
2l/3l > 19/1. 2l, white solid, mp 142–144 °C, 71% yield, 99%
1
NMR (300 MHz, CDCl3) δ 7.26–7.38 (m, 5H), 6.20 (d, J = 1.8 Hz, ee. [Daicel Chiralcel OJ-H (0.46 cm × 25 cm); n-hexane–2-propa-
1H), 5.97–6.10 (m, 2H), 5.22–5.32 (m, 2H), 3.58–3.72 (m, 3H), nol = 85/15; flow rate = 0.4 mL min−1; detection wavelength =
3.39–3.53 (m, 2H), 2.76 (dd, J = 5.4, 12.0 Hz, 1H), 2.66 (dd, J = 254 nm; tR = 14.48 (major), 20.93 (minor) min]. [α]2D0 = −63.9
5.1, 12.9 Hz, 1H).
(c = 1.0, CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.07 (t, J =
2g,12 white solid, 86% yield, 72% ee. [Daicel Chiralpak 7.6 Hz, 1H), 6.64–6.69 (m, 2H), 6.02–6.12 (m, 1H), 5.63 (br s,
AD-H (0.46 cm × 25 cm); n-hexane–2-propanol = 70/30; flow 1H), 5.23–5.28 (m, 2H), 3.72 (AB, JAB = 14.8 Hz, 1H), 3.57–3.63
rate = 0.5 mL min−1; detection wavelength = 214 nm; tR = 21.01 (m, 1H), 3.39 (BA, JBA = 14.8 Hz, 1H), 2.66–2.71 (m, 2H), 2.42
(major), 15.02 (minor) min]. [α]2D0 = −37.5 (c = 0.5, CHCl3). H (s, 3H); 13C NMR (100 MHz, CDCl3) δ 154.5, 140.5, 136.0,
1
NMR (300 MHz, CDCl3) δ 7.28–7.39 (m, 5H), 6.22 (s, 1H), 127.3, 120.9, 118.6, 116.7, 113.8, 58.8, 58.0, 45.8, 39.1; IR
6.02–6.14 (m, 1H), 5.36 (br s, 2H), 5.15–5.23 (m, 2H), 3.86 (s, (film): vmax/cm−1 = 3068, 2977, 2948, 2853, 2818, 2794, 2682,
3H), 3.49–3.71 (m, 4H), 3.35 (d, J = 14.7 Hz, 1H), 2.75 (dd, J = 2357, 1915, 1827, 1737, 1635, 1610, 1587, 1511, 1460, 1446,
3.9, 11.7 Hz, 1H), 2.63 (dd, J = 4.2, 11.4 Hz, 1H).
1416, 1390, 1369, 1346, 1306, 1281, 1260, 1187, 1150, 1128,
3h,12 colorless oil, 73% yield, 21% ee. [Daicel Chiralpak IC 1115, 1080, 1060, 1028, 983, 912, 860, 813, 777, 746, 724, 708,
(0.46 cm × 25 cm); n-hexane–2-propanol = 90/10; flow rate = 639; ESI-HRMS (m/z): exact mass calcd for C12H16NO [M + H]+:
0.6 mL min−1; detection wavelength = 230 nm; tR = 22.66 190.1226. Found: 190.1232.
(major), 10.78 (minor) min]. [α]2D0 = 9.3 (c = 0.5, CHCl3). 1H
2m/3m > 19/1. 2m, white solid, mp 110–112 °C, 91% yield,
NMR (400 MHz, CDCl3) δ 7.25–7.40 (m, 5H), 6.85 (d, J = 8.4 Hz, 84% ee. [Daicel Chiralpak IC (0.46 cm × 25 cm); n-hexane–
1H), 6.79 (d, J = 8.4 Hz, 1H), 5.77–5.87 (m, 1H), 5.05–5.15 (m, 2-propanol = 85/15; flow rate = 0.7 mL min−1; detection wave-
2H), 3.77 (AB, JAB = 14.8 Hz, 1H), 3.73 (s, 3H), 3.72 (s, 2H), 3.59 length = 230 nm; tR = 20.01 (major), 12.79 (minor) min]. [α]D20
=
(BA, JBA = 15.6 Hz, 1H), 3.50–3.55 (m, 1H), 2.84 (dd, J = 5.2, −65.1 (c = 1.0, CHCl3). 1H NMR (400 MHz, CDCl3) δ 6.73 (d, J =
11.2 Hz, 1H), 2.47 (dd, J = 7.6, 11.6 Hz, 1H). 8.0 Hz, 1H), 6.57 (d, J = 8.4 Hz, 1H), 6.04–6.13 (m, 1H), 5.10
3i,12 colorless oil, 61% yield, 3% ee. [Daicel Chiralpak IC (dt, J = 1.6, 10.4 Hz, 1H), 5.05 (dt, J = 1.6, 17.2 Hz, 1H), 3.85 (s,
(0.46 cm × 25 cm); n-hexane–2-propanol = 90/10; flow rate = 3H), 3.79 (AB, JAB = 14.4 Hz, 1H), 3.66–3.67 (m, 1H), 3.22 (BA,
0.5 mL min−1; detection wavelength = 230 nm; tR = 8.94 JBA = 14.4 Hz, 1H), 2.84 (dd, J = 2.8, 11.6 Hz, 1H), 2.50 (dd, J =
(major), 11.60 (minor) min]. [α]2D0 = −2.9 (c = 0.5, CHCl3). 1H 4.4, 11.2 Hz, 1H), 2.40 (s, 3H); 13C NMR (100 MHz, CDCl3)
NMR (300 MHz, CDCl3) δ 7.27–7.44 (m, 5H), 7.03 (d, J = 8.7 Hz, δ 144.5, 143.4, 140.7, 128.3, 121.9, 117.0, 114.5, 109.0, 58.5,
1H), 6.87 (d, J = 8.4 Hz, 1H), 5.75–5.88 (m, 1H), 5.53 (br s, 57.8, 56.0, 46.4, 38.2; IR (film): vmax/cm−1 = 3673, 2972, 2903,
1H), 5.07–5.16 (m, 2H), 3.57–3.74 (m, 4H), 3.47–3.55 (m, 2349, 2325, 1610, 1494, 1456, 1438, 1410, 1378, 1326, 1284,
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