Page 5 of 7
Organic & Biomolecular Chemistry
Please do not adjust margins
Journal Name
ARTICLE
1
(S)‐1‐(6‐Chlorobenzofuran‐2‐yl)‐2‐nitroethanol (6i)
DOI: 10.1039/C6OB02569B
1.99 Hz, 1H), 7.41 (d, J = 7.96 Hz, 1H), 7.30 (dd, J = 2.24, 8.86 Hz, 1H),
Yellow solid; 212 mg, 88%; 1H NMR (CDCl3, 500MHz) 7.51‐7.47 (m,
2H), 7.26 (dd, J = 1.75, 8.35Hz, 1H), 6.80 (t, J = 0.80 Hz, 1H), 5.62
(ddd, J = 0.57, 4.35, 7.68 Hz, 1H), 4.85 (dd, J = 7.75, 13.65 Hz, 1H),
4.82 (dd, J = 4.38, 13.65 Hz, 1H), 3.27 (br s, 1H); 13C NMR (CDCl3, 126
MHz) 155.0, 154.1, 130.9, 126.2, 124.1, 122.0, 112.0, 104.8, 78.2,
65.3; IR (film): 3439(br) 2924, 1556, 1467, 1423, 1380, 1277, 1056
cm‐1; HRMS (ESI): m/z calcd for C10H8ClNO4 [M+Na]+ 264.0040,
found 264.0042; HPLC (Chiralpak AD‐H, 90:10 Hex:iPrOH, 1.0
mL/min, 30 ºC, 208 nm): tr (major) = 19.2 min, tr (minor) = 16.7 min,
85% ee; []D20 ‐38.5 (c 1.0 in CH2Cl2).
6.78 (t, J = 0.81 Hz, 1H), 5.63 (dd, J = 5.24, 6.69 Hz, 1H), 4.85 (dd, J =
7.25, 13.75 Hz, 1H), 4.53 (dd, J = 4.80, 13.75 Hz, 1H), 3.20 (br s, 1H);
13C NMR (CDCl3, 126 MHz) 154.8, 153.3, 128.9, 128.9, 125.3, 121.1,
112.4, 104.5, 78.2, 65.3; IR (film): 3417(br), 2922, 1552, 1446, 1378,
1258, 1176, 1135, 1060 cm‐1; HRMS (ESI): m/z calcd for C10H8ClNO4
[M+Na]+ 264.0040, found 264.0040; HPLC (Chiralpak AD‐H, 95:5
Hex:iPrOH, 1.2 mL/min, 30 ºC, 213 nm): tr (major) = 34.6 min, tr
(minor) = 33.2 min, 89% ee; []D20 ‐31.8 (c 1.0 in CH2Cl2).
(S)‐1‐(3‐methylbenzofuran‐2‐yl)‐2‐nitroethanol (6n)
(S)‐1‐(5‐Methylbenzofuran‐2‐yl)‐2‐nitroethanol (6j)
Yellow solid, 133 mg, 60%; 1H NMR (CDCl3, 500MHz) 7.54 (ddd, J =
0.63, 1.23, 7.67 Hz, 1H), 7.46 (dt, J = 0.75, 8.20 Hz, 1H), 7.36 (ddd, J
= 1.35, 7.27, 8.32 Hz, 1H), 7.29 (td, J = 0.80, 7.51 Hz, 1H), 5.70 (dd, J
= 3.71, 9.20 Hz, 1H), 5.02 (dd, J = 9.20, 13.54 Hz, 1H), 4.71 (dd, J =
3.71, 13.54 Hz, 1H), 2.34 (s, 3H); 13C NMR (CDCl3, 126 MHz) 154.1,
147.4, 129.3, 125.3, 122.9, 119.9, 114.6, 111.33, 78.2, 63.5, 7.8; IR
(film): 3531(br), 2924, 1556, 1455, 1380, 1249, 1188, 1062 cm‐1;
HRMS (ESI): m/z calcd for C11H11NO4 [M+Na]+ 244.0580, found
244.0580; HPLC (Chiralcel OD‐H, 90:10 Hex:iPrOH, 1.0 mL/min, 30
ºC, 250 nm): tr (major) = 24.9 min, tr (minor) = 47.3 min, 98% ee;
[]D20 ‐23.3 (c 1.0 in CH2Cl2).
1
Yellow oil, 171 mg, 77%; H NMR (CDCl3, 500MHz) 7.39‐7.35 (m,
2H), 7.15 (dd, J = 1.38, 8.41 Hz, 1H), 6.74 (t, J =0.80 Hz, 1H), 5.62
(ddd, J = 0.60, 3.72, 8.41 Hz, 1H), 4.86 (dd, J = 8.50, 13.60 Hz, 1H),
4.812 (dd, J =3.80, 13.60 Hz, 1H), 2.46 (s, 3H);13C NMR (CDCl3, 126
MHz) 153.4, 153.3, 132.9, 127.6, 126.3, 121.3, 110.9, 104.6, 78.4,
65.5, 21.3; IR (film): 3484(br), 2918, 1575, 1382, 1263, 1193, 1118,
1095 cm‐1; HRMS (ESI): m/z calcd for C11H11NO4 [M+Na]+ 244.0586,
found 244.0581; HPLC (Chiralpak AD‐H, 90:10 Hex:iPrOH, 1.2
mL/min, 30 ºC, 245 nm): tr (major) = 12.5 min, tr (minor) = 13.3 min,
89% ee; []D20 ‐39.4 (c 1.0 in CH2Cl2).
(S)‐1‐(3‐ethylbenzofuran‐2‐yl)‐2‐nitroethanol (6o)
(S)‐1‐(5‐Ethylbenzofuran‐2‐yl)‐2‐nitroethanol (6k)
1
Yellow oil, 130 mg, 55%; H NMR (CDCl3, 500MHz) 7.59 (ddd, J =
1
Yellow oil, 146 mg, 62%; H NMR (CDCl3, 500MHz) 7.41‐7.38 (m,
0.64, 1.22, 7.66 Hz, 1H), 7.47 (dt, J = 0.80, 8.20 Hz, 1H), 7.35 (ddd, J
= 1.34, 7.26, 8.32 Hz, 1H), 7.30‐7.26 (m, 1H), 5.69 (dd, J = 3.79, 9.19
Hz, 1H), 5.02 (dd, J = 9.19, 13.47 Hz, 1H), 4.70 (dd, J = 3.79, 13.47 Hz,
1H), 2.82 (dd, J = 1.16, 7.64 Hz, 1H), 2.79 (dd, J = 0.99, 7.60 Hz, 1H),
1.33 (t, J = 7.61 Hz, 3H) ; 13C NMR (CDCl3, 126 MHz) 154.3, 146.9,
128.4, 125.2, 122.8, 120.8, 120.2, 111.5, 78.4, 63.4, 16.7, 14.9;
HRMS (ESI): m/z calcd for C12H13NO4 [M+Na]+ 258.0737, found
258.0741; IR (film): 3527(br), 2971, 2933, 1556, 1456, 1379, 1246,
1061 cm‐1; HPLC (Chiralcel OD‐H, 90:10 Hex:iPrOH, 1.0 mL/min, 30
ºC, 250 nm): tr (major) = 19.3 min, tr (minor) = 25.8 min, 97% ee;
[]D20 ‐15.0 (c 1.0 in CH2Cl2).
2H), 7.18 (dd, J = 1.81, 8.44 Hz, 1H), 6.76 (t, J = 0.76 Hz, 1H), 5.62
(ddd, J = 0.67, 3.71, 8.47 Hz, 1H), 4.86 (dd, J = 8.50, 13.60 Hz, 1H),
4.82 (dd, J = 3.75, 13.60 Hz, 1H), 2.76 (q, J = 7.60 Hz, 2H), 1.30 (t, J =
7.60 Hz, 3H); 13C NMR (CDCl3, 126 MHz) 153.5(4), 153.4(7), 139.5,
127.7, 125.3, 120.1, 111.0, 104.7, 78.4, 65.5, 28.8, 16.2; IR (film):
3519(br), 2964, 1556, 1471, 1378, 1195, 1120 cm‐1; HRMS (ESI): m/z
calcd for C12H13NO4 [M+Na]+ 258.0742, found 258.0748; HPLC
(Chiralpak AD‐H, 90:10 Hex:iPrOH, 1.2 mL/min, 30 ºC, 245 nm): tr
(major) = 15.7 min, tr (minor) = 14.6 min, 98% ee; []D20 ‐36.7 (c 1.0
in CH2Cl2).
(S)‐1‐(5‐Fluorobenzofuran‐2‐yl)‐2‐nitroethanol (6l)
(S)‐2‐nitro‐1‐(3‐phenethylbenzofuran‐2‐yl)ethanol (6p)
Yellow solid, 185 mg, 82%; 1H NMR (CDCl3, 500MHz) 7.41 (dd, J =
4.04, 8.95 Hz, 1H), 7.25 (dd, J = 2.60, 8.33 Hz, 1H), 7.06 (m, 1H), 6.80
(t, J = 0.77 Hz, 1H), 5.63 (dd, J = 4.69, 7.02 Hz, 1H), 4.86 (dd, J = 7.45,
1
Yellow oil, 249 mg, 80%; H NMR (CDCl3, 500MHz) 7.64 (ddd, J =
0.65, 1.32, 7.58 Hz, 1H), 7.47 (dt, J = 0.80, 8.00 Hz, 1H), 7.40‐7.36 (m,
1H), 7.33 (td, J = 1.11, 7.65 Hz, 1H), 7.28‐7.23 (m, 2H), 7.22‐7.18 (m,
1H), 7.02‐6.97 (m, 2H), 5.10 (dd, J = 3.33, 9.58 Hz, 1H), 4.65 (dd, J =
9.60, 13.65 Hz, 1H), 3.81 (dd, J = 3.33, 13.65 Hz, 1H), 3.16‐3.07 (m,
2H), 3.06‐2.97 (m, 2H); 13C NMR (CDCl3, 126 MHz) 154.5, 148.5,
141.1, 129.0, 128.6, 128.1, 126.5, 125.4, 123.0, 120.0, 117.1, 111.7,
77.7, 62.9, 35.3, 25.6; IR (film): 3543(br), 3027, 2926, 1556, 1454,
1378, 1250, 1078 cm‐1; HRMS (ESI): m/z calcd for C18H17NO4
[M+Na]+ 334.1050, found 334.1055; HPLC (Chiralpak AD‐H, 95:5
Hex:iPrOH, 1.0 mL/min, 30 ºC, 254 nm): tr (major) = 33.3 min, tr
(minor) = 28.0 min, 96% ee; []D20 ‐36.6 (c 1.0 in CH2Cl2).
13.60 Hz, 1H), 4.82 (dd, J = 4.60, 13.60 Hz, 1H), 3.18 (br s, 1H); 13
C
NMR (CDCl3, 126 MHz) 159.4 (d, JC‐F = 239.5 Hz), 155.2, 151.2,
128.4 (d, JC‐F = 10.9 Hz), 112.8 (d, JC‐F = 26.5 Hz), 112.1 (d, JC‐F = 9.7
Hz), 107.0 (d, JC‐F = 25.2 Hz), 105.0 (d, JC‐F = 3.9 Hz), 78.3, 65.4; IR
(film): 3450(br), 2924, 1555, 1470, 1448, 1380, 1185 cm‐1; HRMS
(ESI): m/z calcd for C10H8FNO4 [M+Na]+ 248.0335, found 248.0329;
HPLC (Chiralpak AD‐H, 95:5 Hex:iPrOH, 1.0 mL/min, 30 ºC, 208 nm):
20
tr (major) = 35.8 min, tr (minor) = 33.5 min, 77% ee; []D ‐29.2 (c
1.0 in CH2Cl2).
(S)‐1‐(5‐Chlorobenzofuran‐2‐yl)‐2‐nitroethanol (6m)
(S)‐1‐(6‐methoxy‐3‐methylbenzofuran‐2‐yl)‐2‐nitroethanol (6q)
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1‐3 | 5
Please do not adjust margins