2400
Y.-H. Liao et al. / Tetrahedron: Asymmetry 20 (2009) 2397–2402
J = 13.2, 8.4 Hz, 1H), 6.20 (d, J = 8.1 Hz, 2H), 7.26 (d, J = 9.0 Hz, 2H),
7.44–7.58 (m, 4H), 7.63–7.72 (m, 2H), 8.01 (d, J = 7.8 Hz, 1H), 8.10
(d, J = 7.8 Hz, 1H); 13C NMR (CDCl3, 75 MHz) d 46.0, 53.2, 76.2,
112.3, 118.0, 127.1, 127.6, 128.0, 128.2, 128.3, 128.6, 129.3, 131.7,
140.1, 141.5, 183.0. HPLC conditions: Chiralcel AS-H column,
i-PrOH/hexane 20:80, flow rate 1.0 mL/min, UV detection at
254 nm, tmajor = 10.42 min, tminor = 12.69 min.
132.6, 133.1, 134.1, 138.4, 138.7, 141.1, 182.9. IR (KBr)
m
1662,
4.2.13. 9-(2-Nitro-1-m-tolylethyl)anthracen-10(9H)-one 4m
1601, 1551, 1317, 933 cmꢀ1. HRMS (ESI) Calcd for C23H16N2NaO3
(M+Na)+: 391.1053; Found: 391.1047. HPLC conditions: Chiralcel
AS-H column, i-PrOH/hexane 30:70, flow rate 1.0 mL/min, UV detec-
tion at 254 nm, tmajor = 26.01 min, tminor = 32.03 min.
White solid, yield 87%; 91% ee, ½a D20
¼ þ33:2 (c 0.60, CHCl3); Mp
ꢁ
111.5–113.9 °C. 1H NMR (CDCl3, 300 MHz) d 2.01 (s, 3H), 3.96–4.02
(m, 1H), 4.51 (d, J = 3.3 Hz, 1H), 4.57 (dd, J = 13.2, 7.2 Hz, 1H), 4.86
(dd, J = 13.2, 9.0 Hz, 1H), 5.77 (s, 1H), 5.86 (d, J = 7.5 Hz, 1H), 6.82–
6.84 (t, J = 7.5 Hz, 1H), 6.94 (d, J = 7.5 Hz, 1H), 7.37–7.44 (m, 2H),
7.50 (d, J = 7.5 Hz, 2H), 7.57–7.64 (m, 2H), 7.97 (d, J = 7.8 Hz, 1H),
8.06 (d, J = 7.8 Hz, 1H); 13C NMR (CDCl3, 75 MHz) d 21.0, 46.1,
53.1, 76.6, 125.4, 126.6, 127.0, 127.6, 127.8, 128.0, 128.1, 128.3,
128.7, 129.5, 132.2, 132.6, 132.8, 133.3, 134.3, 137.5, 139.3,
4.2.9. 9-(1-(2-Bromophenyl)-2-nitroethyl)anthracen-10(9H)-
one 4i
White solid, yield 95%; 83% ee, ½a D20
¼ þ7:1 (c 0.74, CHCl3); Mp
ꢁ
62.8–65.6 °C. 1H NMR ((CD3)2SO, 300 MHz) d 4.02–4.45 (m, 1H),
4.78 (d, J = 5.3 Hz, 1H), 4.92–5.03 (m, 1H), 5.09 (dd, J = 13.8, 5.4 Hz,
1H), 6.59–6.60 (m, 1H), 7.08–7.11 (m, 2H), 7.30–7.38 (m, 2H),
7.49–7.63 (m, 5H), 7.93 (d, J = 7.5 Hz, 1H); 13C NMR ((CD3)2SO,
75 MHz) d 45.5, 50.4, 77.5, 126.4, 126.4, 127.1, 128.0, 128.6, 129.2,
129.4, 129.9, 132.4, 132.6, 132.7, 133.5, 134.7, 140.3, 141.2, 183.2.
141.9, 183.0. IR (KBr)
m
1657, 1601, 1547, 1314, 931 cmꢀ1. HRMS
(ESI) Calcd for C23H19NNaO3 (M+Na)+: 380.1257; Found:
380.1250. HPLC conditions: Chiralcel OD-H column, i-PrOH/hexane
30:70, flow rate 1.0 mL/min, UV detection at 254 nm, tmajor
12.21 min, tminor = 9.50 min.
=
IR (KBr)
m
1662, 1599, 1552, 1317, 932 cmꢀ1. HRMS (ESI) Calcd for
C22H16BrNNaO3 (M+Na)+: 444.0206; Found: 444.0187. HPLC condi-
tions: Chiralcel AS-H column, i-PrOH/hexane 20:80, flow rate
1.0 mL/min, UV detection at 254 nm, tmajor = 10.85 min,
tminor = 13.54 min.
4.2.14. 9-(2-Nitro-1-(3-nitrophenyl)ethyl)anthracen-10(9H)-
one 4n7b
White solid, yield 60%; 90% ee, ½a D20
¼ þ38:1 (c 0.40, CHCl3); Mp
ꢁ
163.0–166.4 °C. 1H NMR ((CD3)2SO, 300 MHz) d 4.12–4.17 (m, 1H),
4.96 (d, J = 3.9 Hz, 1H), 5.06 (dd, J = 13.8, 10.8 Hz, 1H), 5.51 (dd,
J = 14.1, 5.1 Hz, 1H), 6.56 (d, J = 7.8 Hz, 1H), 6.88 (s, 1H), 7.19 (t,
J = 7.8 Hz, 1H), 7.48–7.62 (m, 3H), 7.70–7.87 (m, 5H), 7.96 (d,
J = 8.5 Hz, 1H); 13C NMR ((CD3)2SO, 75 MHz) d 45.0, 52.2, 77.1,
122.4, 123.0, 125.7, 126.2, 127.9, 128.2, 128.8, 129.0, 129.1,
132.4, 132.8, 133.3, 133.4, 135.1, 136.5, 139.0, 142.3, 146.6,
182.5. HPLC conditions: Chiralcel AS-H column, i-PrOH/hexane
4.2.10. 9-(1-(2-Methoxyphenyl)-2-nitroethyl)anthracen-10(9H)-
one 4j
White solid, yield 89%; 89% ee, ½a D20
¼ ꢀ8:6 (c 0.88, CHCl3); Mp
ꢁ
128.5–131.4 °C. 1H NMR ((CD3)2SO, 300 MHz) d 3.21 (s, 1H), 4.42–
4.46 (m, 1H), 4.73 (d, J = 4.0 Hz, 1H), 4.82 (dd, J = 13.2, 10.2 Hz, 1H),
5.12 (dd, J = 13.5, 6.0 Hz, 1H), 6.06 (d, J = 6.6 Hz, 1H), 6.54 (t,
J = 7.5 Hz, 1H), 6.67 (d, J = 8.1 Hz, 1H), 7.09 (t, J = 7.2 Hz, 1H),
7.43–7.54 (m, 4H), 7.62–7.67 (t, J = 7.5 Hz, 2H), 7.85 (d, J = 7.5 Hz,
1H), 7.91 (m, J = 7.8 Hz, 1H); 13C NMR ((CD3)2SO, 75 MHz) d 45.2,
45.5, 55.0, 76.9, 110.5, 119.4, 122.5, 125.7, 126.1, 127.4, 127.7,
128.2, 128.8, 128.9, 129.3, 132.3, 133.3, 140.7, 142.3, 157.1,
20:80, flow rate 1.0 mL/min, UV detection at 254 nm, tmajor
35.48 min, tminor = 42.52 min.
=
4.2.15. 9-(1-(3-Bromophenyl)-2-nitroethyl)anthracen-10(9H)-
one 4o
182.8. IR (KBr)
m
1658, 1602, 1553, 1510, 1317, 932 cmꢀ1. HRMS
White solid, yield 65%; 90% ee, ½a D20
¼ þ31:0 (c 0.58, CHCl3); Mp
ꢁ
(ESI) Calcd for C23H19NNaO4 (M+Na)+: 396.1206; Found:
396.1192. HPLC conditions: Chiralcel AS-H column, i-PrOH/hexane
20:80, flow rate 1.0 mL/min, UV detection at 254 nm, tmajor = 9.75
min, tminor = 11.08 min.
114.7–117.1 °C. 1H NMR (CDCl3, 300 MHz) d 3.97–4.03 (m, 1H),
4.52–4.59 (m, 2H), 4.85 (dd, J = 13.2, 8.7 Hz, 1H), 6.00 (d, J = 7.2 Hz,
1H), 6.14 (s, 1H), 6.82 (t, J = 7.8 Hz, 1H), 7.28 (d, J = 9.0 Hz, 1H),
7.39–7.55 (m, 4H), 7.60–7.67 (m, 2H), 8.01 (d, J = 7.5 Hz, 1H), 8.11
(d, J = 7.6 Hz, 1H); 13C NMR (CDCl3, 75 MHz) d 46.1, 52.9, 76.3,
122.0, 126.9, 127.0, 127.4, 128.0, 128.0, 128.3, 128.4, 129.4, 131.3,
131.7, 132.5, 132.9, 133.3, 134.2, 135.4, 138.8, 141.4, 182.9. IR
4.2.11. 9-(2-Nitro-1-(2-nitrophenyl)ethyl)anthracen-10(9H)-
one 4k
White solid, yield 91%; 90% ee, ½a D20
ꢁ
¼ ꢀ4:0 (c 0.20, CHCl3); Mp
(KBr) m
1656, 1599, 1550, 1315, 931 cmꢀ1. HRMS (ESI) Calcd for
68.1–71.7 °C. 1H NMR ((CD3)2SO, 300 MHz) d 4.71–4.76 (m, 1H)
4.86(d, J = 5.1 Hz, 1H), 5.11 (dd, J = 13.5, 10.2 Hz, 1H), 5.28 (dd,
J = 13.8, 5.4 Hz, 1H), 6.70–6.73 (m, 1H), 7.32–7.40 (m, 3H), 7.50–
7.64 (m, 6H), 7.89 (dd, J = 13.8, 7.5 Hz, 2H); 13C NMR ((CD3)2SO,
75 MHz) d 45.4, 45.7, 77.4, 124.3, 126.4, 126.5, 128.1, 128.2,
128,6, 129.0, 129.1, 129.3, 129.4, 132.1, 132.2, 132.5, 133.0,
C22H16BrNNaO3 (M+Na)+: 444.0206; Found: 444.0199. HPLC condi-
tions: Chiralcel AS-H column, i-PrOH/hexane 20:80, flow rate
1.0 mL/min, UV detection at 254 nm, tmajor = 12.67 min, tminor
14.98 min.
=
4.2.16. 9-(2-Nitro-1-(3-(trifluoromethyl)phenyl)ethyl) anthra-
133.5, 139.7, 141.0, 149.9, 182.9. IR (KBr)
m
1666, 1600, 1553,
cen-10(9H)-one 4p
1526, 1315, 932 cmꢀ1
.
HRMS (ESI) Calcd for C22H16N2NaO5
White solid, yield 65%; 91% ee, ½a D20
¼ þ26:2 (c 0.44, CHCl3); Mp
ꢁ
(M+Na)+: 411.0951; Found: 411.0944. HPLC conditions: Chiralcel
OD-H column, i-PrOH/hexane 30:70, flow rate 1.0 mL/min, UV
detection at 254 nm, tmajor = 13.05 min, tminor = 16.93 min.
147.5–150.4 °C. 1H NMR ((CD3)2SO, 300 MHz) d 4.06–4.11 (m, 1H),
4.93 (d, J = 3.7 Hz, 1H), 5.02 (dd, J = 13.8, 10.5 Hz, 1H), 5.51 (dd,
J = 13.8, 5.1 Hz, 1H), 6.24 (s, 1H), 6.36 (d, J = 7.5 Hz, 1H), 7.11–
7.14 (t, J = 7.8 Hz, 1H) 7.41–7.60 (m, 4H), 7.69–7.79 (m, 4H), 7.87
(d, J = 7.6 Hz, 1H); 13C NMR ((CD3)2SO, 75 MHz) d 45.0, 52.5, 77.2,
116.6, 121.9, 122.5, 123.6, 124.2, 124.3, 124.9, 125.0, 125.4,
125.5, 125.7, 126.2, 126.6, 127.5, 127.7, 127.9, 128.0, 128.4,
128.7, 129.0, 132.3, 132.4, 132.6, 133.0, 133.2, 133.3, 135.3,
4.2.12. 9-(1-(2-Chlorophenyl)-2-nitroethyl)anthracen-10(9H)-
one 4l7b
White solid, yield 96%; 84% ee, ½a D20
¼ ꢀ14:8 (c 0.54, CHCl3); Mp
ꢁ
163.4–165.8 °C. 1H NMR (CDCl3, 300 MHz) d 4.41–4.43 (m, 2H),
4.71–4.75 (m, 2H), 6.26 (d, J = 7.5 Hz, 1H), 6.82 (d, J = 7.2 Hz, 1H),
7.03 (t, J = 7.6 Hz, 1H), 7.21–7.27 (m, 1H), 7.38–7.58 (m, 4H),
7.70–7.73 (m, 2H), 8.20 (t, J = 8.3 Hz, 2H); 13C NMR ((CD3)2SO,
75 MHz) d 45.3, 47.8, 77.4, 126.3, 126.4, 127.9, 128.0, 128.6,
129.0, 129.1, 129.7, 132.3, 132.4, 132.6, 132.7, 133.5, 135.0,
139.1, 142.5, 182.2. IR (KBr)
m .
1665, 1602, 1551, 1324, 932 cmꢀ1
HRMS (ESI) Calcd for C23H16F3NNaO3 (M+Na)+: 434.0974; Found:
434.0967. HPLC conditions: Chiralcel AD-H column, i-PrOH/hexane
10:90, flow rate 1.0 mL/min, UV detection at 254 nm, tmajor
11.05 min, tminor = 11.82 min.
=