334
J. Lv et al. / Tetrahedron: Asymmetry 17 (2006) 330–335
2H); 13C NMR: d 164.6, 139.1, 136.9, 136.8, 130.3,
128.1, 124.8, 123.6, 123.1, 117.4, 110.0, 106.4, 70.7,
69.0, 65.7, 65.0, 61.8, 59.8, 56.4, 38.0, 26.3, 25.7, 21.9.
mined by HPLC analysis, using Chiralpak OD column,
hexane/isopropanol = 95:5, flow rate = 0.5 mL/min,
tR = 79.04 min (2R,3S), tR 89.36 min (2S,3R); 1H
NMR: d 8.30–8.28 (m, 2H), 8.01–7.99 (m, 2H), 7.70–
7.64 (m, 1H), 7.58–7.50 (m, 4H), 4.30 (d, 1H,
J = 1.7 Hz), 4.18 (d, 1H, J = 1.1 Hz).
4.1.3. Polymeric ammonium salt 2b. A light brown
20
solid, mp 45–46 ꢁC; ½aꢁD ¼ ꢀ20:2 (c 0.4, CH2Cl2). IR
(KBr) m 3421, 3210, 3077, 2884, 1677, 1621, 1588,
1560, 1508, 1467, 1359, 1344, 1280, 1241, 1112, 963,
4.2.4.
trans-2,3-Epoxy-3-(4-methylphenyl)-1-phenyl-
20
1
841, 779 cmꢀ1; H NMR: 9.26–9.20 (m, 2H), 8.77 (d,
propan-1-one 6d. Yield: 86%; mp 77–78 ꢁC; ½aꢁD ¼
2H, J = 4.8 Hz), 8.09 (d, 2H, J = 9 Hz), 7.96–7.87 (m,
4H), 7.41–7.37 (m, 2H), 5.62–5.52 (m, 2H), 5.29 (d,
2H, J = 17 Hz), 5.07 (d, 2H, J = 12 Hz), 4.95–4.84 (m,
2H), 4.57–4.51 (m, 2H), 4.09–4.06 (m, 4H), 3.89–3.80
(m, 4H, PEG), 3.66–3.51 (m, PEG), 3.47 (s, 6H), 2.80–
2.70 (m, 4H), 2.18–1.81 (m, 14H), 1.11–0.95 (m, 4H);
13C NMR: d 164.8, 158.6, 137.4, 137.3, 137.0, 131.2,
126.2, 122.9, 120.5, 117.1, 110.0, 101.4, 70.7, 69.0,
66.2, 63.6, 61.7, 59.7, 57.5, 56.9, 37.9, 26.4, 25.8, 22.3.
þ116:7 (c 1, CH2Cl2), 49% ee; enantiomeric excess was
determined by HPLC analysis, using Chiralpak OD col-
umn, hexane/isopropanol = 99:1, flow rate = 0.8 mL/
min, tR = 42.84 min (2R,3S), tR = 45.41 min (2S,3R);
1H NMR: d 8.00 (d, 2H, J = 7.2 Hz), 7.61 (t, 2H,
J = 7.2 Hz), 7.48 (t, 2H, J = 7.2 Hz), 7.28–7.20 (m,
4H), 4.28 (d, 1H, J = 1.8 Hz), 4.04 (d, 1H, J = 1.3 Hz),
2.37 (s, 3H).
4.2.5. trans-2,3-Epoxy-3-(4-chlorophenyl)-1-phenylpropan-
20
4.2. Enantioselective epoxidation of 2,4-diarylenones 5
using 1 or 2, as catalysts under PTC conditions
1-one 6f. Yield: 93%; mp 64–66 ꢁC; ½aꢁD ¼ þ66:7
(c 1, CH2Cl2), 33% ee; enantiomeric excess was deter-
mined by HPLC analysis, using Chiralpak OD column,
hexane/isopropanol = 95:5, flow rate = 1.0 mL/min,
tR = 19.63 min (2R,3S), tR = 21.57 min (2S,3R); 1H
NMR: d 8.03–8.01 (m, 2H), 7.68–7.65 (m, 1H), 7.54–
7.50 (m, 2H), 7.35–7.31 (m, 2H), 7.21–7.26 (m, 2H),
4.30 (d, 1H, J = 1.5 Hz), 4.05 (d, 1H, J = 1.5 Hz).
To a stirred mixture of 5 (0.125 lmol), polymeric catal-
yst 1, or 2 (6.25 lmol) in the appropriate solvent
(4 mL) at the selected temperature (see Table 1), was
added the corresponding oxidant (H2O2, 30%, 0.2 mL;
t-BuOOH, 70%, 0.07mL; cumylhydroperoxide, 70%,
0.08mL; NaOCl, 10%, 0.1 mL). The corresponding base
was then added after 10 min. The reaction mixture was
stirred vigorously at the selected temperature until the
starting material had been consumed (TLC, 48 h). The
mixture was diluted with dichloromethane (15 mL),
washed with water (2 · 10 mL), dried over MgSO4, fil-
tered off, and evaporated in vacuo. Diethyl ether
(25 mL) was added in the residue, shaken, and then
stilled. The polymeric catalyst was filtered and
reclaimed. The solution was evaporated in vacuo. Puri-
fication of the residue by flash column chromatography
on silica gel (hexane–ethyl acetate, 10:1) afforded the
pure product 6.
4.2.6.
trans-2,3-Epoxy-1-(4-methoxyphenyl)-3-phenyl-
20
propan-1-one 6g. Yield: 77%; mp 78–80 ꢁC; ½aꢁD
¼
þ73:7 (c 1, CH2Cl2), 35% ee; enantiomeric excess was
determined by HPLC analysis, using Chiralpak AD-H
column, hexane/isopropanol = 95:5, flow rate =
0.8 mL/min, tR = 38.924 min (2R,3S), tR = 42.60 min
1
(2S,3R); H NMR: d 8.02–8.00 (d, 2H), 7.41–7.36 (m,
5H), 6.94–6.96 (m, 2H), 4.30 (d, 1H, J = 2.0 Hz), 4.06
(d, 1H, J = 2.0 Hz), 3.90 (s, 3H).
4.2.7. trans-2,3-Epoxy-4-methylbutanophenone 6j. Yield:
20
85%, a colorless oil; ½aꢁD ¼ þ5:0 (c 1, CH2Cl2), 19% ee;
enantiomeric excess was determined by HPLC analysis,
using Chiralpak OD-H column, hexane/isopropa-
nol = 95:5, flow rate = 0.5 mL/min, tR = 11.47 min
(2R,S), tR = 13.36 min (2S,3R); 1H NMR: d 8.02 (d,
2H, J = 8.6 Hz), 7.66–7.58 (m, 1H), 7.56–7.47 (m, 2H),
4.07 (d, 1H, J = 2.0 Hz), 2.97 (dd, 1H, J = 2.0, 6.0 Hz);
1.84–1.72 (m, 1H), 1.11 (d, 3H, J = 6.9 Hz), 1.07 (d,
3H, J = 6.9 Hz).
4.2.1. trans-2,3-Epoxy-1,3-diphenylpropan-1-one 6a.
20
Yield: 90%; mp 74–75 ꢁC; ½aꢁD ¼ þ177:4 (c 1, CH2Cl2),
86% ee; enantiomeric excess was determined by HPLC
analysis, using Chiralpak OD column, hexane/isopropa-
nol = 95:5, flow rate = 0.8 mL/min, tR = 24.92 min
(2R,3S), tR = 27.24 min (2S,3R); 1H NMR: d 8.02–
8.00 (m, 2H), 7.65–7.38 (m, 8H), 4.30 (d, 1H, J = 1.5
Hz), 4.09 (d, 1H, J = 1.5 Hz).
Acknowledgements
4.2.2. trans-2,3-Epoxy-3-(3-nitrophenyl)-1-phenylpropan-
20
1-one 6b. Yield: 72%; mp 115–116 ꢁC, ½aꢁD ¼ þ142:5
This work was financially supported by 973Project (No.
2002CB211800, China) and the National Natural
Science Foundation of China (Grant No. 20472032,
China). We also thank Nankai University, State Key
Laboratory of Elemento-Organic Chemistry, for
support.
(c 1, CH2Cl2), 57% ee; enantiomeric excess was deter-
mined by HPLC analysis, using Chiralpak OD column,
hexane/isopropanol = 95:5, flow rate = 0.6 mL/min,
tR = 59.73 min (2R,3S), tR = 68.85 min (2S,3R); 1H
NMR: d 8.03 (d, 2H, J = 7.2 Hz), 7.73 (d, 1H,
J = 7.6 Hz), 7.66–7.61 (m, 2H), 7.54–7.50 (m, 2H),
4.32 (d, 1H, J = 1.5 Hz), 4.22 (d, 1H, J = 1.5 Hz).
References
4.2.3. trans-2,3-Epoxy-3-(4-nitrophenyl)-1-phenylpropan-
20
1-one 6c. Yield: 55%; mp 138–140 ꢁC, ½aꢁD ¼ þ140:6
1. Katsuki, T.; Sharpless, K. B. J. Am. Chem. Soc. 1980, 102,
5974–5976.
(c 1, CH2Cl2), 57% ee; enantiomeric excess was deter-