Z. Rapi et al. / Tetrahedron: Asymmetry 22 (2011) 1189–1196
1193
4.2.4. trans-(ꢀ)-2,3-Epoxy-1-(2-furyl)-3-(4-chlorophenyl)-prop-
1H), 4.16 (d, J = 1.5 Hz, 1H), 4.03 (d, J = 1.5 Hz, 1H). HRMS calcd
for C13H9FO2S 248.0307, found 248.0311.
an-1-one 5d
Yield: 67%; ½a 2D2
¼ ꢀ146:5 (c 1, CHCl3) 62% ee; mp 102–103 °C;
ꢁ
1H NMR (CDCl3, 500 MHz) d (ppm): 7.68 (d, J = 1.5 Hz, 1H), 7.45 (d,
J = 3.5 Hz, 1H), 7.37 (d, J = 8.5 Hz, 2H), 7.28 (d, J = 8.5 Hz, 2H), 6.60
(dd, J = 3.5 Hz, 1.5 Hz, 1H), 4.13 (d, J = 1.5 Hz, 1H), 4.10 (d,
4.2.12. (2R,3S)-2,3-Epoxy-1-(2-thienyl)-3-(2-tolyl)-propan-1-
one 7f
Yield: 79%; ½a 2D2
ꢁ
¼ ꢀ45:7 (c 1, CH2Cl2) 68% ee; mp 72–74 °C; 1H
J = 1.5 Hz, 1H). HRMS calcd for
C
13H9ClO3 248.0240, found
NMR (CDCl3, 500 MHz), d (ppm): 8.03 (dd, J = 4 Hz, 1 Hz, 1H), 7.75
(dd, J = 5 Hz, 1 Hz, 1H), 7.30 (dd, J = 7 Hz, 2 Hz, 1H), 7.27–7.23 (m,
2H), 7.19 (t, J = 4.5 Hz, 1H), 7.18–7.17 (m, 1H), 4.29 (d, J = 1.5 Hz,
1H), 3.98 (d, J = 1.5 Hz, 1H), 2.37 (s, 3H). HRMS calcd for
248.0242.
4.2.5. trans-(ꢀ)-2,3-Epoxy-1-(2-furyl)-3-pyperonyl-propan-1-
one 5e
C14H12O2S 244.0558, found 244.0563.
Yield: 45%; ½a 2D2
ꢁ
¼ ꢀ151:3 (c 1, CHCl3) 64% ee; mp 82–84 °C; 1H
NMR (CDCl3, 300 MHz) d (ppm): 7.67 (d, J = 1.5 Hz, 1H), 7.45 (d,
J = 3.5 Hz, 1H), 6.86 (d, J = 8.1 Hz, 1H), 6.80 (d, J = 8.1 Hz, 1H),
6.77 (s, 1H), 6.60 (dd, J = 3.5 Hz, 1.5 Hz, 1H), 5.99 (s, 2H), 4.09 (d,
J = 1.5 Hz, 1H), 4.07 (d, J = 1.5 Hz, 1H). HRMS calcd for C14H10O5
258.0528, found 258.0525.
4.2.13. trans-(+)-2,3-Epoxy-1-(2-thienyl)-3-(1-naphthyl)-prop-
an-1-one 7g
Yield: 87%; ½a 2D2
ꢁ
¼ þ54 (c 1, CH2Cl2) 64% ee; mp 108–110 °C; 1H
NMR (CDCl3, 300 MHz), d (ppm): 8.03 (d, J = 3.5 Hz, 1H), 8.01–7.99
(m, 1H), 7.92–7.89 (m, 1H), 7.86 (d, J = 8 Hz, 1H), 7.77 (dd, J = 5 Hz,
1 Hz, 1H), 7.58 (d, J = 7.5 Hz, 1H), 7.54–7.51 (m, 2H), 7.49 (d,
J = 7.5 Hz, 1H), 7.19 (t, J = 4.5 Hz, 1H), 4.80 (d, J = 1.5 Hz, 1H), 4.11
(d, J = 1.5 Hz, 1H). HRMS calcd for C17H12O2S 280.0558, found
280.0554.
4.2.6. trans-(ꢀ)-2,3-Epoxy-1-(2-furyl)-3-(2-naphthyl)-propan-1-
one 5f
Yield: 30%; ½a 2D2
¼ ꢀ73:6 (c 1, CHCl3) 28% ee; mp 114–117 °C;
ꢁ
1H NMR (CDCl3, 500 MHz) d (ppm): 7.88–7.82 (m, 4H), 7.67 (d,
J = 1.5 Hz, 1H), 7.53–7.50 (m, 2H), 7.47 (d, J = 3.5 Hz, 1H), 7.38
(dd, J = 8.5 Hz, 1.5 Hz, 1H), 6.59 (dd, J = 3.5 Hz, 1.5 Hz, 1H), 4.32
(d, J = 1.5 Hz, 1H), 4.24 (d, J = 1.5 Hz, 1H). HRMS calcd for
4.2.14. trans-(ꢀ)-2,3-Epoxy-1-(2-thienyl)-3-(2-naphthyl)-prop-
an-1-one 7h
Yield: 54%; ½a 2D2
ꢁ
¼ ꢀ163 (c 1, CH2Cl2) 62% ee; Oil; 1H NMR
C17H12O3 264.0786, found 264.0784.
(CDCl3, 500 MHz), d (ppm): 8.02 (d, J = 3 Hz, 1H), 7.90–7.82 (m,
4H), 7.75 (d, J = 4.8 Hz, 1H), 7.54–7.79 (m, 2H), 7.38 (d, J = 8.7 Hz,
1H), 7.18 (t, J = 4.2 Hz, 1H), 4.34 (d, J = 1.5 Hz, 1H), 4.18 (d,
4.2.7. trans-(ꢀ)-2,3-Epoxy-1-(2-thienyl)-3-phenylpropan-1-one
7a
J = 1.5 Hz, 1H). HRMS calcd for C17H12O2S 280.0558, found
280.0561.
Yield: 63%; ½a 2D2
ꢁ
¼ ꢀ169:8 (c 1, CH2Cl2) 71% ee; mp 49–50 °C; 1H
NMR (CDCl3, 500 MHz), d (ppm): 8.00 (d, J = 3.5 Hz, 1H), 7.73 (d,
J = 5 Hz, 1H), 7.39–7.37 (m, 3H), 7.35–7.33 (m, 2H), 7.17 (t,
J = 4.5 Hz, 1H), 4.17 (d, J = 1.5 Hz, 1H), 4.07 (d, J = 1.5 Hz, 1H). HRMS
calcd for C13H10O2S 230.0402, found 230.0406.
4.2.15. (2R,3S)-2,3-Epoxy-1-(2-thienyl)-3-piperonyl-propan-1-
one 7i
Yield: 57%; ½a 2D2
¼ ꢀ131:5 (c 1, CH2Cl2) 86% ee; After crystalliza-
ꢁ
tion: ½a 2D2
ꢁ
¼ ꢀ268:8 (c 1, CH2Cl2) 100% ee; mp 108–110 °C; 1H NMR
4.2.8. trans-(ꢀ)-2,3-Epoxy-1-(2-thienyl)-3-(2-chlorophenyl)-
(CDCl3, 500 MHz), d (ppm): 8.00 (d, J = 4 Hz, 1H), 7.74 (d, J = 5 Hz,
1H), 7.17 (t, J = 4.5 Hz, 1H), 6.86 (d, J = 8.1 Hz, 1H), 6.80 (d,
J = 8.1 Hz, 1H), 6.77 (s, 1H), 5.98 (s, 2H), 4.09 (d, J = 1.5 Hz, 1H),
4.02 (d, J = 1.5 Hz, 1H). HRMS calcd for C14H10O4S 274.0300, found
274.0306.
propan-1-one 7b
Yield: 53%; ½a 2D2
ꢁ
¼ ꢀ10 (c 1, CH2Cl2) 51% ee; mp 49–50 °C; 1H
NMR (CDCl3, 300 MHz), d (ppm): 8.02 (d, J = 3 Hz, 1H), 7.76 (d,
J = 4.8 Hz, 1H), 7.29–7.21 (m, 4H), 7.19 (t, J = 3.9 Hz, 1H), 4.49 (d,
J = 1.5 Hz, 1H), 3.97 (d, J = 1.5 Hz, 1H). HRMS calcd for C13H9ClO2S
264.0012, found 264.0008.
4.2.16. trans-(ꢀ)-2,3-Epoxy-1-(3-thienyl)-3-phenylpropan-1-
one 9a
4.2.9. trans-(ꢀ)-2,3-Epoxy-1-(2-thienyl)-3-(3-chlorophenyl)-
Yield: 53%; ½a 2D2
ꢁ
¼ ꢀ72:2 (c 1, CH2Cl2) 52% ee; mp 91–93 °C; 1H
propan-1-one 7c
NMR (CDCl3, 500 MHz), d (ppm): 8.37 (dd, J = 2.5 Hz, 1 Hz, 1H),
7.65 (dd, J = 5 Hz, 1 Hz, 1H), 7.40 (dd, J = 5 Hz, 3 Hz, 1H), 7.39–
7.36 (m, 3H), 7.36–7.33 (m, 2H), 4.11 (d, J = 1.5 Hz, 1H), 4.06 (d,
Yield: 56%; ½a 2D2
ꢁ
¼ ꢀ142:1 (c 1, CH2Cl2) 60% ee; mp 78–80 °C; 1H
NMR (CDCl3, 500 MHz), d (ppm): 8.00 (dd, J = 3.5 Hz, 1 Hz, 1H),
7.76 (dd, J = 5 Hz, 1 Hz, 1H), 7.34 (s, 1H), 7.34–7.30 (m, 1H), 7.31
(d, J = 8 Hz, 1H), 7.25–7.23 (m, 1H), 7.19 (t, J = 4.5 Hz, 1H), 4.15
(d, J = 1.5 Hz, 1H), 4.04 (d, J = 1.5 Hz, 1H). HRMS calcd for
J = 1.5 Hz, 1H). HRMS calcd for
C13H10O2S 230.0402, found
230.0399.
C
13H9ClO2S 264.0012, found 264.0007.
4.2.17. trans-(ꢀ)-2,3-Epoxy-1-(3-thienyl)-3-(2-tolyl)-propan-1-
one 9b
4.2.10. trans-(ꢀ)-2,3-Epoxy-1-(2-thienyl)-3-(4-chlorophenyl)-
Yield: 51%; ½a 2D2
ꢁ
¼ ꢀ19:3 (c 1, CH2Cl2) 52% ee; mp 72–74 °C; 1H
propan-1-one 7d
NMR (CDCl3, 500 MHz), d (ppm): 8.39 (dd, J = 2.5 Hz, 1 Hz, 1H),
7.67 (dd, J = 5 Hz, 1 Hz, 1H), 7.37 (dd, J = 5 Hz, 3 Hz, 1H), 7.30 (dd,
J = 8 Hz, 2.5 Hz, 1H), 7.23–7.26 (m, 2H), 7.16–7.19 (m, 1H), 4.24
(d, J = 1.5 Hz, 1H), 3.96 (d, J = 1.5 Hz, 1H), 2.35 (s, 3H). HRMS calcd
for C14H12O2S 244.0558, found 244.0562.
Yield: 54%; ½a 2D2
ꢁ
¼ ꢀ139 (c 1, CH2Cl2) 65% ee; mp 80–82 °C; 1H
NMR (CDCl3, 500 MHz), d (ppm): 8.00 (d, J = 3.5 Hz, 1H), 7.75 (d,
J = 5 Hz, 1H), 7.37 (d, J = 8 Hz, 2H), 7.28 (d, J = 8 Hz, 2H), 7.18 (t,
J = 4.5 Hz, 1H), 4.15 (d, J = 1.5 Hz, 1H), 4.02 (d, J = 1.5 Hz, 1H). HRMS
calcd for C13H9ClO2S 264.0012, found 264.0014.
4.2.18. trans-(ꢀ)-2,3-Epoxy-1-(3-thienyl)-3-(1-naphthyl)-prop-
4.2.11. trans-(ꢀ)-2,3-Epoxy-1-(2-thienyl)-3-(4-fluorophenyl)-
an-1-one 9c
propan-1-one 7e
Yield: 66%; ½a 2D2
ꢁ
¼ þ51:9 (c 1, CH2Cl2) 54% ee; Oil. 1H NMR
Yield: 55%; ½a 2D2
ꢁ
¼ ꢀ119:7 (c 1, CH2Cl2) 62% ee; mp 64–66 °C; 1H
(CDCl3, 500 MHz), d (ppm): 8.40 (dd, J = 3 Hz, 1 Hz, 1H), 8.00–
7.97 (m, 1H), 7.93–7.89 (m, 1H), 7.86 (d, J = 8.5 Hz, 1H), 7.72 (dd,
J = 5 Hz, 1 Hz, 1H), 7.59 (d, J = 7.5 Hz, 1H), 7.54–7.51 (m, 2H), 7.49
(d, J = 7.5 Hz, 1H), 7.38 (dd, J = 5 Hz, 3 Hz, 1H), 4.74 (d, J = 1.5 Hz,
NMR (CDCl3, 500 MHz), d (ppm): 8.01 (d, J = 3.5 Hz, 1H), 7.75 (d,
J = 4.5 Hz, 1H), 7.33 (d, J = 5.5 Hz, 1H), 7.31 (d, J = 5.5 Hz, 1H),
7.18 (t, J = 4.5 Hz, 1H), 7.09 (d, J = 3.5 Hz, 1H), 7.07 (d, J = 3.5 Hz,