600
K. Zilbeyaz et al. / Tetrahedron: Asymmetry 23 (2012) 594–601
4.5.5. (R)-1-(p-Methylphenyl)ethanol 3e23
4.5.12. (S)-[1-(p-Biphenyl)]ethyl hydroperoxide 4f
Obtained as a colourless oil. ½a D25
ꢃ
¼ þ41:9 (c 0.375, MeOH); IR
Obtained as a white solid. Mp 68–70 °C, ½a D25
¼ ꢀ79:2 (c 0.457,
ꢃ
mmax (KBr, cmꢀ1): 3362, 2973, 1514, 1451, 1370, 1088, 1011, 899;
1H NMR (200 MHz, CDCl3): d 7,27 (d, J = 8.2 Hz, 2H), 7.17 (d,
J = 8.2 Hz, 2H), 4.87 (q, J = 6.4 Hz, 1H), 2.35 (s, 3 H), 1.90 (br s,
1H), 1.49 (d, J = 6.4 Hz, 3H); 13C NMR (50 MHz, CDCl3): d 142.9,
137.0, 129.1, 125.4, 70.1, 25.1, 21.1; HPLC (Chiral OB-H column,
i-PrOH–hexane, 10/90, 0.6 mL/min): tR (R) 13.5 min and (S)
11.8 min.
CH2Cl2); IR m
max (KBr, cmꢀ1) = 3400, 3030, 2976, 2930, 1669, 1607,
1484, 1407, 1361, 1292, 1192, 1076, 1007; 1H NMR (200 MHz,
CDCl3): d 7,98 (br s, 1H), 7.69-7.35 (m, 9H), 5.16 (q, J = 6.6 Hz,
1H), 1.55 (d, J = 6.6 Hz, 3H); 13C NMR (50 MHz, CDCl3): d 142.2,
141.7, 141.3, 129.8 (2 ꢂ C), 128.4, 128.1, 128.0, 84.4, 21.0; HPLC
(Chiral OB-H column, i-PrOH–hexane, 10/90, 0.6 mL/min): tR (S)
20.9 min and (R) 19.8 min.
4.5.6. (R)-1-(p-Biphenyl)ethanol 3f22
4.6. Epoxidation
Obtained as a white solid. Mp 93–95 °C. ½a D25
¼ þ47:0 (c 0.550,
ꢃ
CH2Cl2); IR mmax (KBr, cmꢀ1): 3346, 3030, 2981, 1607, 1464, 1353,
1192, 1085, 1010; 1H NMR (200 MHz, CDCl3): d 7.64–7.33 (m,
9H), 4.60 (q, J = 7.6 Hz, 1H), 2.10 (br s, 1H), 1.56 (d, J = 7.6 Hz,
3H); 13C NMR (50 MHz, CDCl3): d 145.8, 141.8, 141.3, 129.7
(2 ꢂ C), 128.2, 128.0, 126.8, 71.1, 26.1; HPLC (Chiral OD column,
i-PrOH–hexane, 10/90, 0.6 mL/min): tR (R) 17.6 min and (S)
16.4 min.
General epoxide synthesis: To a stirred solution of chalcone
(93 mg, 0.45 mmol) and hydroperoxide (0.5 mmol) in 5 mL solvent
was added solid KF-Al2O3 (80 mg, 0.5 mmol). The reaction was fol-
lowed by TLC and upon completion the mixture was filtered to re-
move KF-Al2O3. The solvent was removed under reduced pressure
and the crude product purified by column chromatography.
4.7. Chalcone epoxide 626
4.5.7. (S)-(1-Phenyl)ethyl hydroperoxide 4a1,25
Obtained as a colourless oil. ½a D25
¼ ꢀ103 (c 0.065, CHCl3); IR
ꢃ
Obtained as a white solid. Mp 81–83 °C (lit. mp 82–84 °C). IR
mmax (KBr, cmꢀ1) = 3061, 3030, 1692, 1600, 1500, 1453, 1415,
1353, 1292, 1230, 1184, 1076, 1015; 1H NMR (200 MHz, CDCl3):
d 7.70 (m, 10 H), 4.30 (d, J = 1.9 Hz, 1H), 4.09 (d, J = 1.9 Hz, 1H);
13C NMR (50 MHz, CDCl3): d 194.9, 137.5, 135.9, 131.0, 130.8,
130.7, 130.3, 127.7, 98.1, 63.0, 61.3; HPLC (Chiral OD column,
mmax (KBr, cmꢀ1): 3401, 3062, 3031, 2985, 2931, 1604, 1496,
1450, 1373, 1303, 1211, 1211, 1072; 1H NMR (200 MHz, CDCl3):
d 8.43 (br s, 1H), 7.41-7.35 (m, 5H), 5.09 (q, J = 6.9 Hz, 1H), 1.51
(d, J = 6.9 Hz, 3H); 13C NMR (50 MHz, CDCl3): d 141.6, 128.8,
128.4, 126.7, 84.0, 20.2; HPLC (Chiral OD column, i-PrOH–hexane,
10/90, 0.6 mL/min): tR (S) 18.4 min and (R) 15.1 min.
i-PrOH–hexane, 10/90, 0.6 mL/min): tR
and ( R,bS) 22.9 min (minor).
(aS,bR) 21.5 min (major)
a
4.5.8. (S)-[1-(p-Fluoro)phenyl]ethyl hydroperoxide 4b
Obtained as a colourless oil. ½a D25
¼ ꢀ68:6 (c 0.454, CH2Cl2); IR
ꢃ
mmax (KBr, cmꢀ1): 3420, 2970, 2921, 1610, 1512, 1475, 1378,
1223, 1112, 1095, 1017; 1H NMR (200 MHz, CDCl3): d 8.08 (br s,
1H), 7.35–7.31 (m, 2H), 7.06 (m, 2H), 5.04 (q, J = 6.6 Hz, 1H), 1.45
(d, J = 6.6 Hz, 3H); 13C NMR (50 MHz, CDCl3): d 128.6, 128.5,
115.8, 115.6, 83.2, 20.2; HPLC (Chiral OB-H column, i-PrOH–hex-
ane, 10/90, 0.6 mL/min): tR (S) 15.5 min and (R) 17.3 min.
Acknowledgment
This study was financially supported by Ataturk University.
References
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Casteel, D. A. Nat. Prod. Rep. 1999, 16, 55.
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4.5.9. (S)-[1-(p-Chloro)phenyl]ethyl hydroperoxide 4c8
Obtained as a colourless oil; ½a D25
¼ ꢀ84:1 (c 0.45, MeOH); IR
ꢃ
mmax (KBr, cmꢀ1): 3415, 2961, 2923, 2861, 1607, 1500, 1469,
1407, 1376, 1307, 1207, 1100, 1015; 1H NMR (200 MHz, CDCl3):
d 7.35-7.32 (m, 4H), 5.05 (q, J = 6.6 Hz, 1H), 1.40 (d, J = 6.6 Hz,
3H); 13C NMR (50 MHz, CDCl3): d 141.9, 135.9, 130.7, 129.9, 84.9,
21.9; HPLC (Chiral OB-H column, i-PrOH–hexane, 10/90, 0.6 mL/
min): tR (S) 14.7 min and (R) 21.6 min.
6. Adam, W.; Lazarus, M.; Hoch, U.; Korb, M. N.; Saha-Möller, C. R.; Schreier, P. J.
Org. Chem. 1998, 63, 6123.
7. Adam, W.; Heckel, F.; Saha-Möller, C. R.; Schreier, P. J. Organomet. Chem. 2002,
661, 17.
4.5.10. (S)-[1-(p-Bromo)phenyl]ethyl hydroperoxide 4d
Obtained as a colourless oil. ½a D25
¼ ꢀ65:8 (c 0.594, CH2Cl2); IR
ꢃ
8. (a) Adam, W.; Lazarus, M.; Saha-Möller, C. R.; Weichold, O.; Hoch, U.; Häring,
D.; Schreier, P. Biotransformations with Peroxidases In Advances in Biochemical
Engineering/Biotechnology; Faber, K., Ed.; Springer: Heidelberg, 1999; Vol. 63, p
73; (b) Adam, W.; Hoch, U.; Lazarus, M.; Saha-Möller, C. R.; Schreier, P. J. Am.
Chem. Soc. 1995, 117, 11898.
mmax (KBr, cmꢀ1): 3400, 2984, 2930, 1592, 1492, 1453, 1407,
1369, 1300, 1207, 1130, 1076, 1015; 1H NMR (200 MHz, CDCl3):
d 8.25 (br s, 1H), 7.51 (d, J = 8.3 Hz, 2H), 7.24 (d, J = 8.3 Hz, 2H),
5.01 (q, J = 6.6 Hz, 1H), 1.44 (d, J = 6.6 Hz, 3H); 13C NMR (50 MHz,
CDCl3): d 142.5, 133.7, 130.3, 124.0, 85.0, 21.9; HPLC (Chiral OB-
H column, i-PrOH–hexane, 10/90, 0.6 mL/min): tR (S) 15.5 min
and (R) 23.9 min.
9. Fu, H.; Kondo, H.; Ichikawa, Y.; Look, G. C.; Wong, C.-H. J. Org. Chem. 1992, 57,
7265.
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4.5.11. (S)-[1-(p-Methyl)phenyl]ethyl hydroperoxide 4e
Obtained as a colourless oil. ½a D25
¼ ꢀ68:6 (c 0.542, CH2Cl2); IR
ꢃ
mmax (KBr, cmꢀ1): 3412, 3040, 2948, 2922, 1620, 1532, 1450,
1378, 1249, 1120, 1095; 1H NMR (200 MHz, CDCl3): d 7,72 (br s,
1H), 7,28 (d, J = 7.8 Hz, 2H), 7.20 (d, J = 7.8 Hz, 2H), 5.06 (q,
J = 6.6 Hz, 1H), 2.37 (s, 3 H), 1.48 (d, J = 6.6 Hz, 3H); 13C NMR
(50 MHz, CDCl3): d 132.1, 131.9, 128.7, 117.2, 85.7, 31.7, 22.5;
HPLC (Chiral OD-H column, i-PrOH–hexane, 10/90, 0.6 mL/min):
tR (S) 12.8 min and (R) 10.5 min.