(1H, m, CHAr), 2.65 (1H, m, CHCO), 2.48 (1H, m, chex-H),
2.32 (2H, m, chex-H), 2.09 (1H, m, chex-H), 1.70 (4H, m,
chex-H), 1.21 (1H, m, chex-H). HPLC: Daicel Chiralpak
AD-H. Hexane–i-PrOH, 95 : 5, 1 mL min−1, 230 nm: tR
(major) = 25 min; tR (minor) = 19 min.
2.11 (1H, m, chex-H), 1.83–1.43 (4H, m, chex-H), 1.25 (1H,
m, chex-H); 13C NMR (100 MHz, CDCl3) d = 211.4, 150.3,
149.7, 136.0, 134.0, 124.1, 78.5, 52.6, 43.1, 42.0, 33.5, 28.7,
25.5. m/z (ES) found 249.1246 ([MH+] C13H17N2O3 requires
249.1239. HPLC: Daicel Chiralpak AD. Hexane–i-PrOH, 88 :
12, 1 mL min−1, 254 nm: tR (major) = 26 min; tR (minor) =
35 min.
(2S,1ꢀR)-2-[2ꢀ-Nitro-1ꢀ-(o-furanyl)-ethyl]-cyclohexanone26 29a.
Purified using flash column chromatography (EtOAc–petroleum
ether 40/60, 3 : 17) to give the title compound as a yellow solid
(3S,1ꢀR)-3-(2ꢀ-Nitro-1ꢀ-(m-nitrophenyl)-ethyl)-tetrahydro-thio-
pyran-4-one 34a. Purified using flash column chromatography
(EtOAc–petroleum ether 40/60, 3 : 7) to yield the title compound
as a white solid (96.1 mg, 62%). mmax (film)/cm−1 2925, 1701,
1558, 1525, 1347, 734, 686. 1H NMR (600 MHz, CDCl3)
d = 8.19 (2H, m, ArH), 7.60 (2H, m, ArH), 4.82 (1H, m,
CHHꢀNO2), 4.68 (1H, m, CHHꢀNO2), 4.18 (1H, m, CHAr),
3.10 (1H, m, CHCHAr), 2.99 (2H, m, C(O)CH2), 2.84 (2H,
m, C(O)CH2CH2), 2.58 (1H, m, CHCHHꢀS), 2.48 (1H, m,
CHCHHꢀS). 13C NMR (150 MHz, CDCl3) d = 208.4, 148.2,
139.0, 134.6, 130.4, 123.4, 123.0, 77.9, 54.7, 44.6, 43.3, 35.0,
31.5. m/z (EI) found 310.0613 ([M]+ C13H14N2O5S requires
310.0623). HPLC: Daicel Chiralpak AD-H. Hexane–i-PrOH,
90 : 10, 1 mL min−1, 254 nm: tR (major) = 51 min; tR (minor) =
28 min.
1
(69.9 mg, 59%). H NMR (400 MHz, CDCl3) d = 7.33 (1H,
d, J = 1.1 Hz, ArH), 6.28 (1H, dd, J = 2.8, 1.1 Hz, ArH),
6.17 (1H, d, J = 2.8 Hz, ArH), 4.78 (1H, dd, J = 12.5, 4.8 Hz,
CHHꢀNO2), 4.67 (1H, dd, J = 12.5, 9.3 Hz, CHHꢀNO2), 3.99
(1H, m, CHAr), 2.77 (1H, m, CHC(O)), 2.51–2.35 (2H, m, chex-
H), 2.15 (1H, m, chex-H), 1.95–1.62 (4H, m, chex-H), 1.35 (1H,
m, chex-H). HPLC: Daicel Chiralpak AD-H. Hexane–i-PrOH,
95 : 5, 0.5 mL min−1, 230 nm: tR (major) = 25 min; tR (minor) =
32 min.
(2S,1ꢀR)-2-[2ꢀ -Nitro-1ꢀ -(m-nitro-phenyl)-ethyl]-cyclohexa-
none24 30a. Purified using flash column chromatography
(EtOAc–petroleum ether 40/60, 1 : 3) to give the title compound
1
as a yellow solid (135 mg, 92%). H NMR (600 MHz, CDCl3)
d = 8.12 (1H, d, J = 7.9 Hz, ArH), 8.07 (1H, s, ArH), 7.55
(1H, d, J = 7.7 Hz, ArH), 7.50 (1H, m, ArH), 4.99 (1H, dd,
J = 13.1, 4.4 Hz, CHHꢀNO2), 4.71 (1H, dd, J = 13.1, 10.2 Hz,
CHHꢀNO2), 3.92 (1H, m, CHAr), 2.74 (1H, m, CHC(O)), 2.46
(1H, m, chex-H), 2.40 (1H, m, chex-H), 2.09 (1H, m, chex-H),
1.80 (1H, m, chex-H), 1.76–1.55 (3H, m, chex-H), 1.24 (1H, m,
chex-H). HPLC: Daicel Chiralpak AD. Hexane–i-PrOH, 95 :
5, 0.5 mL min−1, 230 nm: tR (major) = 99 min; tR (minor) =
82 min.
(3R,1ꢀS)-3-(2ꢀ-Nitro-1ꢀ-(m-nitrophenyl)-ethyl)-tetrahydro-thio-
pyran-4-one 35a. Purified using flash column chromatography
(EtOAc–petroleum ether 40/60, 3 : 7) to yield the title compound
as a white solid (104 mg, 67%). mmax (film)/cm−1 2925, 1701,
1558, 1525, 1347, 734, 686. 1H NMR (600 MHz, CDCl3)
d = 8.19 (2H, m, ArH), 7.60 (2H, m, ArH), 4.82 (1H, m,
CHHꢀNO2), 4.68 (1H, m, CHHꢀNO2), 4.18 (1H, m, CHAr),
3.10 (1H, m, CHCHAr), 2.99 (2H, m, C(O)CH2), 2.84 (2H,
m, C(O)CH2CH2), 2.58 (1H, m, CHCHHꢀS), 2.48 (1H, m,
CHCHHꢀS). 13C NMR (150 MHz, CDCl3) d = 208.4, 148.2,
139.0, 134.6, 130.4, 123.4, 123.0, 77.9, 54.7, 44.6, 43.3, 35.0,
31.5. m/z (EI) found 310.0613 ([M]+ C13H14N2O5S requires
310.0623). HPLC: Daicel Chiralpak AD-H. Hexane–i-PrOH,
90 : 10, 1 mL min−1, 254 nm: tR (major) = 29 min; tR (minor) =
51 min.
(2S,1ꢀR)-2-[2ꢀ -Nitro-1ꢀ-(o-thiophenyl)-ethyl]-cyclohexanone27
31a. Purified using flash column chromatography (EtOAc–
petroleum ether 40/60, 3 : 17) to yield the title compound as a
1
white solid (94.0 mg, 74%). H NMR (400 MHz, CDCl3) d =
7.21 (1H, d, J = 4.9 Hz, ArH), 6.93 (1H, dd, J = 5.1, 3.6 Hz,
ArH), 6.87 (1H, d, J = 3.0 Hz, ArH), 4.89 (1H, dd, J = 12.6,
4.8 Hz, CHHꢀNO2), 4.67 (1H, dd, J = 12.6, 9.3 Hz, CHHꢀNO2),
4.15 (1H, m, CHAr), 2.71 (1H, m, CHC(O)), 2.58–2.35 (2H,
m, chex-H), 2.12 (1H, m, chex-H), 1.97–1.82 (2H, m, chex-H),
1.76–1.55 (2H, m, chex-H), 1.35 (1H, m, chex-H). HPLC:
Daicel Chiralpak AD. Hexane–i-PrOH, 95 : 5, 1 mL min−1, 230
nm: tR (major) = 20 min; tR (minor) = 23 min.
(3S,1ꢀR)-3-[2ꢀ -Nitro-1ꢀ -(m-nitrophenyl)-ethyl]-tetrahydro-py-
ran-4-one 36a. Purified using flash column chromatography
(EtOAc–petroleum ether 40/60, 4 : 6) to yield the title compound
as a yellow solid (138 mg, 94%). mmax (film)/cm−1 2865, 1706,
1
1549, 1531, 1344. H NMR (600 MHz, CDCl3) d = 8.19 (1H,
(2S,1ꢀR)-2-[2ꢀ-Nitro-1ꢀ-(p-trifluoromethylphenyl)-ethyl]-cyclo-
hexanone 32a. Purified using flash column chromatography
(EtOAc–petroleum ether 40/60, 1 : 4) to yield the title
compound as a white solid (91.4 mg, 58%). Mp = 92–94 ◦C,
mmax (film)/cm−1: 2944, 1707, 1551, 1258, 1216, 1162. 1H NMR
(600 MHz, CDCl3) d = 7.31–7.15 (4H, dd, J = 19.8, 8.8 Hz,
ArH), 4.92 (1H, dd, J = 12.8, 4.8 Hz, CHHꢀNO2), 4.63 (1H,
dd, J = 12.4, 9.9 Hz, CHHꢀNO2), 3.82 (1H, m, CHAr), 2.69
(1H, m, CHC(O)), 2.46 (1H, m, chex-H), 2.38 (1H, m, chex-H),
2.09 (1H, m, chex-H), 1.83–1.56 (4H, m, chex-H), 1.26 (1H,
m, chex-H). 13C NMR (150 MHz, CDCl3) d = 211.8, 149.1,
136.9, 130.0, 121.7, 121.7, 78.9, 52.9, 43.7, 43.1, 33.5, 28.8, 25.5.
m/z (FAB+) found 354.0924 ([MNa]+ C15H16NO4F3Na requires
354.0924). HPLC: Daicel Chiralpak AD. Hexane–i-PrOH, 95
: 5, 1 mL min−1, 230 nm: tR (major) = 17 min; tR (minor) =
26 min.
dt, J = 7.2, 1.8 Hz, ArH), 8.11 (1H, s, ArH), 7.57 (2H, m,
ArH), 5.01 (1H, dd, J = 13.2, 4.4 Hz, CHHꢀNO2), 4.71 (1H,
dd, J = 13.2, 10.3 Hz, CHHꢀNO2), 4.20 (1H, m, CHCH2C(O)),
3.98 (1H, m, CHAr), 3.80–3.66 (2H, m, CHC(O)CHHꢀCH2),
3.28 (1H, dd, J = 11.4, 9.4 Hz, C(O)CHHꢀCH2), 2.95 (1H,
CHC(O)), 2.71 (1H, m, CHHꢀC(O)), 2.58 (1H, m, CHHꢀC(O)).
13C NMR (150 MHz, CDCl3) d = 206.3, 149.0, 138.7, 134.3,
130.32, 123.4, 122.7, 78.0, 71.3, 69.0, 52.8, 43.0, 41.0. m/z (EI)
found 294.0861 ([M]+ C13H14N2O6 requires 294.0861). HPLC:
Daicel Chiralpak AD-H. Hexane–i-PrOH, 90 : 10, 1 mL min−1,
254 nm: tR (major) = 50 min; tR (minor) = 33 min.
(3S,4R)-3-Methyl-5-nitro-4-(m-nitrophenyl)-pentan-2-one37a.
Purified using flash column chromatography (EtOAc–petroleum
ether 40–60, 3 : 7) to yield the title compound as a white solid
(94.4 mg, 71%). mmax (film)/cm−1 2865, 1706, 1549, 1531, 1344,
(2S,1ꢀR)-2-[2ꢀ -Nitro-1ꢀ -(o-pyridinyl)-ethyl]-cyclohexanone
33a. Purified using flash column chromatography (EtOAc–
petroleum ether 40/60, 13 : 7) to yield the title compound
as a yellow oil (58.5 mg, 47%). mmax (film)/cm−1 2944, 1705,
1548, 1428, 1378, 1130, 716. 1H NMR (400 MHz, CDCl3)
d = 8.53–8.45 (2H, m, ArH), 7.55 (1H, dt, J = 7.8, 1.8 Hz,
ArH), 7.27 (1H, m, ArH), 4.92 (1H, dd, J = 12.8, 4.4 Hz,
CHHꢀNO2), 4.69 (1H, dd, J = 12.8, 9.9 Hz, CHHꢀNO2), 3.80
(1H, m, CHAr), 2.72 (1H, m, CHC(O)), 2.46 (2H, m, chex-H),
689. H NMR (600 MHz, CDCl3) d = 8.17 (1H, m, ArH),
1
8.08 (1H, s, ArH), 7.54 (2H, d, J = 5.1 Hz, ArH), 4.70 (2H,
m, CH2NO2), 3.85 (1H, m, CHAr), 3.03 (1H, m, CHC(O)),
2.27 (3H, s, CH3C(O)), 1.01 (3H, d, J = 7.2 Hz, CH3CH).
13C NMR (150 MHz, CDCl3) d = 209.7, 148.6, 139.9, 134.5,
130.1, 123.1, 122.8, 77.8, 48.6, 45.4, 29.2, 16.0. m/z (ES) found
267.0975 ([MH]+ C12H15N2O5 requires 267.0975). HPLC: Daicel
Chiralpak AD-H. Hexane–i-PrOH, 90 : 10, 1 mL min−1, 254 nm:
tR (major) = 16 min; tR (minor) = 13 min.
9 4
O r g . B i o m o l . C h e m . , 2 0 0 5 , 3 , 8 4 – 9 6