D.-Q. Xu et al. / Tetrahedron: Asymmetry 18 (2007) 1788–1794
1793
[PF6]ꢁ; HRMS (ESI): Calcd for PFꢁ: 144.9642. Found:
144.9646.
10.4 Hz, 1H), 3.79 (s, 3H), 3.77–3.70 (m, 1H), 2.70–2.62
(m, 1H), 2.49–2.35 (m, 2H), 2.10–2.07 (m, 1H), 1.81–1.55
(m, 4H), 1.27–1.21 (m, 1H); MS (EI): 55 (5), 77 (16), 91
(26), 103 (14), 121 (39), 134 (27), 147 (11), 159 (18), 171
(10), 187 (14), 201 (100), 213 (33), 230 (38), 277 (19).
6
4.3.5. (S)-(+)-1-Pyrrolidin-2-ylmethyl-quinolinium bromide
hydrobromide 4. 1H NMR (400 MHz, DMSO-d6, d ppm):
10.29 (s, 1H), 9.26 (s, 2H), 8.96–8.94 (d, J = 8.0 Hz, 1H),
8.72–8.70 (d, J = 8.0 Hz, 1H), 8.52–8.50 (d, J = 8.0 Hz,
1H), 8.41–8.39 (d, J = 8.0 Hz, 1H), 8.33–8.29 (t,
J = 8.0 Hz, 1H), 8.13–8.10 (t, J = 8.0 Hz, 1H), 5.22–5.19
(m, 2H), 4.30–4.28 (m, 1H), 3.38–3.34 (m, 1H), 3.22–3.19
(m, 1H), 2.29–2.22 (m, 1H), 2.11–2.04 (m, 1H), 1.98–1.83
(m, 2H); 13C NMR (75 MHz, DMSO-d6, d ppm): 151.4,
137.8, 137.7, 135.4, 131.8, 131.1, 127.7, 127.6, 126.5, 59.9,
59.8, 45.3, 28.0, 22.9; IR (KBr): 3405, 2704, 2394, 1568,
1433, 1210 cmꢁ1; MS (ESI, m/z): 213.0 [MꢁHBr–Br]+;
HRMS (ESI): Calcd for C14H17Nþ2 : 213.1392. Found:
213.1388.
4.3.10. 2-(2-Nitro-1-(4-methoxyphenyl)ethyl)cyclohexanone
8d. The ee value was determined by HPLC analysis (Daicel
Chiralpak AS-H, hexane/2-propanol = 85/15, 1.0 ml/min,
1
220 nm; tr(minor) = 18.76 min, tr(major) = 20.07 min); H
NMR (400 MHz, CDCl3, d ppm): 7.09 (d, J = 6.7 Hz, 2H),
6.85 (d, J = 6.7 Hz, 2H), 4.90 (dd, J = 12.4, 4.6 Hz, 1H),
4.58 (dd, J = 12.4, 9.6 Hz, 1H), 3.78 (s, 3H), 3.71 (ddd,
J = 9.6, 9.6, 4.6 Hz, 1H), 2.72–2.60 (m, 1H), 2.50–2.31 (m,
2H), 2.11–2.02 (m, 1H), 1.77–1.64 (m, 4H), 1.27–1.15 (m,
1H); MS (EI): 55 (4), 77 (6), 91 (14), 103 (5), 121 (39), 134
(74), 147 (6), 176 (5), 187 (7), 201 (100), 213 (6), 230 (54),
277 (3).
4.3.6. (S)-(+)-10-Pyrrolidin-2-ylmethyl-acridinium bromide
hydrobromide 5. 1H NMR (400 MHz, DMSO-d6, d ppm):
9.99 (s, 1H), 8.88–8.72 (m, 2H), 8.53–8.51 (d, J = 8.0 Hz,
2H), 8.41–8.38 (d, J = 8.0 Hz, 2H), 8.30–8.26 (t,
J = 8.0 Hz, 2H), 7.95–7.91 (t, J = 8.0 Hz, 2H), 4.48-4.43
(m, 1H), 3.59–3.56 (m, 1H), 3.29–3.15 (m, 2H), 3.00–2.98
(m, 1H), 2.23–2.20 (m, 1H), 1.94–1.85 (m, 2H), 1.75–1.71
(m, 1H); 13C NMR (75 MHz, DMSO-d6, d ppm): 148.3,
140.7, 137.4, 130.3, 128.1, 126.2, 120.8, 49.3, 44.4, 42.8,
32.6, 21.7; IR (KBr): 3429, 2995, 2897, 2705, 2415, 1638,
1583, 1467, 1398, 892, 746 cmꢁ1; MS (ESI, m/z): 263.2
4.3.11. 2-(2-Nitro-1-(4-methylphenyl)ethyl)cyclohexanone
8e. The ee value was determined by HPLC analysis (Dai-
cel Chiralpak AS-H, hexane/2-propanol = 85/15, 1.0 ml/
min, 220 nm; tr(minor) = 8.56 min, tr(major) = 13.33 min);
1H NMR (400 MHz, CDCl3, d ppm): 7.12 (d, J = 8.4 Hz,
2H), 7.04 (d, J = 8.4 Hz, 2H), 4.91 (dd, J = 12, 4.8 Hz,
1H), 4.60 (dd, J = 12, 10 Hz, 1H), 3.75–3.69 (ddd,
J = 10, 10, 4.8 Hz, 1H), 2.70–2.63 (m, 1H), 2.50–2.35 (m,
2H), 2.33 (s, 3H), 2.10–2.04 (m, 1H), 1.79–1.52 (m, 4H),
1.28–1.18 (m, 1H); MS (EI): 55 (6), 77 (7), 91 (17), 105
(47), 118 (36), 129 (16), 147 (13), 155 (11), 171 (11), 185
(100), 197 (13), 214 (53).
[MꢁHBr–Br]+; HRMS (ESI): Calcd for C18H19Nþ:
2
263.1548. Found: 263.1545.
4.3.7. 2-(2-Nitro-1-phenylethyl)cyclohexanone 8a. ee value
was determined by HPLC analysis (Daicel Chiralpak AS-
H, hexane/2-propanol = 85/15, 1.0 ml/min, 220 nm; tr(mi-
nor) = 14.32 min, tr(major) = 20.58 min); 1H NMR
(400 MHz, CDCl3, d ppm): 7.34–7.16 (m, 5H), 4.95 (dd,
J = 12.4, 4.8 Hz, 1H), 4.63 (dd, J = 12.4, 10 Hz, 1H),
3.75 (ddd, J = 10, 10, 4.8 Hz, 1H), 2.72–1.19 (m, 9H, cycl);
MS (EI): 55 (30), 77 (12), 91 (63), 104 (34), 115 (25), 141
(15), 157 (13), 171 (100), 183 (21), 200 (60), 247 (1).
4.3.12.
2-(2-Nitro-1-(4-chlorophenyl)ethyl)cyclohexanone
8f. The ee value was determined by HPLC analysis (Daicel
Chiralpak AS-H, hexane/2-propanol = 85/15, 1.0 ml/min,
220 nm; tr(minor) = 11.18 min, tr(major) = 17.47 min); H
1
NMR (400 MHz, CDCl3, dppm): 7.34 (d, J = 8.4 Hz, 2H),
7.15 (d, J = 8.4 Hz, 2H), 4.93 (dd, J = 12.4, 4.4 Hz, 1H),
4.61 (dd, J = 12.4, 10 Hz, 1H), 3.75 (ddd, J = 10, 10,
4.4 Hz, 1H), 2.67–2.63 (m, 1H), 2.50–2.34 (m, 2H), 2.10–
2.08 (m, 1H), 1.82–1.61 (m, 4H), 1.30–1.19 (m, 1H); MS
(EI): 55 (13), 77 (10), 89 (7), 103 (16), 115 (23), 125 (57),
138 (37), 151 (11), 165 (12), 175 (7), 182 (8), 191 (13), 205
(100), 217 (14), 234 (50).
4.3.8. 2-(2-Nitro-1-(2-methoxyphenyl)ethyl)cyclohexanone
8b. The ee value was determined by HPLC analysis (Dai-
cel Chiralpak AS-H, hexane/2-propanol = 85/15, 1.0 ml/
min, 220 nm; tr(minor) = 11.35 min, tr(major) = 14.90 -
min); 1H NMR (400 MHz, CDCl3, d ppm): 7.24 (dd,
J = 8.4, 7.6 Hz, 1H), 7.08 (d, J = 7.6 Hz, 1H), 6.88 (t,
J = 8.4 Hz, 2H), 4.88–4.80 (m, 2H), 3.95 (dt, J = 9.2,
4.9 Hz, 1H), 3.84 (s, 3H), 3.01–2.94 (m, 1H), 2.49–2.35
(m, 2H), 2.09–2.05 (m, 1H), 1.79–1.56 (m, 4H), 1.25–1.16
(m, 1H); MS (EI): 55 (11), 77 (17), 91 (15), 105 (11), 121
(60), 134 (54), 145 (10), 159 (12), 171 (9), 187 (7), 201
(100), 213 (6), 230 (51), 277 (10).
4.3.13.
2-(2-Nitro-1-(2-bromophenyl)ethyl)cyclohexanone
8g. The ee value was determined by HPLC analysis (Daicel
Chiralpak AS-H, hexane/2-propanol = 85/15, 1.0 ml/min,
220 nm; tr(minor) = 10.54 min, tr(major) = 13.67 min); H
NMR (400 MHz, CDCl3, d ppm): 7.47 (dd, J = 8.1,
1.2 Hz, 1H), 7.23–7.13 (m, 2H), 7.06–7.00 (m, 1H), 4.87–
4.73 (m, 2H), 4.30–4.22 (m, 1H), 2.78 (m, 1H), 2.38–2.28
(m, 2H), 2.03–1.97 (m, 1H), 1.72–1.45 (m, 4H), 1.30–1.26
(m, 1H); MS (EI): 55 (14), 67 (5), 77 (14), 91 (7), 103 (16),
115 (26), 128 (23), 141 (8), 155 (7), 171 (24), 185 (96), 199
(18), 246 (100).
1
4.3.9. 2-(2-Nitro-1-(3-methoxyphenyl)ethyl)cyclohexanone
8c. The ee value was determined by HPLC analysis (Daicel
Chiralpak AS-H, hexane/2-propanol = 85/15, 1.0 ml/min,
4.3.14.
2-(2-Nitro-1-(3-bromophenyl)ethyl)cyclohexanone
1
220 nm; tr(minor) = 12.75 min, tr(major) = 25.90 min); H
8h. The ee value was determined by HPLC analysis (Daicel
NMR (400 MHz, CDCl3, d ppm): 7.25 (t, J = 8.0 Hz, 1H),
6.79 (d, J = 8.0 Hz, 1H), 6.75 (d, J = 8.0 Hz, 1H), 6.71 (s,
1H), 4.92 (dd, J = 12.0, 4.0 Hz, 1H), 4.62 (dd, J = 12.0,
Chiralpak AS-H, hexane/2-propanol = 85/15, 1.0 ml/min,
220 nm; tr(minor) = 12.22 min, tr(major) = 21.42 min); H
NMR (400 MHz, CDCl3, d ppm): 7.27 (s, 1H), 7.19 (d,
1