Chiral Bioinspired Non-Heme Iron Complexes for Enantioselective Epoxidation of a,b-Unsaturated Ketones
J=7.6 Hz, 2H, ArH), 7.64 (t, J=7.6 Hz, 1H, ArH), 7.50 (t,
J=7.6 Hz, 2H, ArH), 7.39 (d, J=8.4 Hz, 2H, ArH), 7.31 (d,
J=8.4 Hz, 2H, ArH), 4.26 (d, J=1.6 Hz, 1H, CH), 4.07 (d,
J=1.6 Hz, 1H, CH); 13C NMR (100 MHz, CDCl3): d 192.7,
135.4, 135.0, 134.1, 134.0, 129.0, 128.9, 128.4, 127.1, 60.9,
58.7; HPLC (Chiralcel OJ, 208C, 254 nm, 90/10 hexane/i-
PrOH, 1.0 mLminꢀ1): tmajor =20.59 min, tminor =30.00 min.
trans-(2S,3R)-Epoxy-3-(2-chlorophenyl)-1-phenylpropan-
1-one: Yield: 80%; 1H NMR (400 MHz, CDCl3): d=8.06
(dd, J1 =1.2 Hz, J2 =8.4 Hz, 2H, ArH), 7.64 (t, J=10.0 Hz,
1H, ArH), 7.51 (t, J=7.2 Hz, 2H, ArH), 7.42–7.40 (m, 2H,
ArH), 7.34–7.32 (m, 2H, ArH), 4.41 (d, J=2.0 Hz, 1H,
CH), 4.18 (d, J=2.0 Hz, 1H, CH); 13C NMR (100 MHz,
CDCl3): d=192.8, 135.3, 134.1, 133.8, 133.3, 129.8, 129.3,
128.9, 128.4, 127.3, 126.1, 60.1, 57.2; HPLC (Chiralcel AD-
10 hexane/i-PrOH, 1.0 mLminꢀ1): tmajor =14.63 min, tminor
=
12.10 min.
trans-(2S,3R)-Epoxy-3-phenyl-1-(4-methylphenyl)-
1
propan-1-one: Yield: 61%; H NMR (400 MHz, CDCl3): d=
7.92 (d, J=8.0 Hz, 2H, ArH), 7.43–7.35 (m, 5H, ArH), 7.28
(d, J=8.4 Hz, 2H, ArH), 4.27 (d, J=2.0 Hz, 1H, CH), 4.07
(d, J=1.6 Hz, 1H, CH), 2.42 (s, 3H, CH3); 13C NMR
(100 MHz, CDCl3): d=192.6, 145.1, 135.6, 133.0, 129.6,
129.0, 128.8, 128.8, 125.8, 60.9, 59.3, 21.8; HPLC (Chiralcel
OB-H, 208C, 254 nm, 90/10 hexane/i-PrOH, 1.0 mLminꢀ1):
tmajor =20.90 min, tminor =27.43 min.
trans-Epoxy-3-(4-fluorophenyl)-1-(4-methylphenyl)-
1
propan-1-one: Yield: 84%; H NMR (400 MHz, CDCl3): d=
7.91 (d, J=8.0 Hz, 2H, ArH), 7.36–7.28 (m, 4H, ArH),
7.11–7.07 (m, 2H, ArH), 4.23 (d, J=2.0 Hz, 1H, CH), 4.06
(d, J=1.6 Hz, 1H, CH), 2.43 (s, 3H, CH3); 13C NMR
(100 MHz, CDCl3): d=192.4, 164.4, 162.0, 145.2, 133.0,
131.5, 131.4, 129.6, 128.5, 127.6, 127.5, 116.0, 115.7, 60.9,
58.7, 21.8; HPLC (Chiralcel OJ, 208C, 254 nm, 90/10
H, 208C, 254 nm, 99/1 hexane/iPrOH, 1.0 mLminꢀ1): tmajor
22.22 min, tminor =19.59 min.
=
trans-(2S,3R)-Epoxy-3-(2-bromophenyl)-1-phenylpropan-
1
1-one: Yield: 63%; H NMR (400 MHz, CDCl3): d=8.06 (d,
hexane/i-PrOH, 1.0 mLminꢀ1):
tmajor =17.46 min, tminor =
J=3.2 Hz, 2H, ArH), 7.64–7.58 (m, 2H, ArH), 7.51 (t, J=
7.6 Hz, 2H, ArH), 7.40–7.38 (m, 2H, ArH), 7.28–7.26 (m,
1H, ArH), 4.36 (d, J=1.6 Hz, 1H, CH), 4.17 (d, J=1.6 Hz,
1H, CH); 13C NMR (100 MHz, CDCl3): d=192.8, 135.4,
135.3, 134.1, 132.5, 130.1, 128.9, 128.5, 127.8, 126.5, 122.5,
60.0, 59.4; HPLC (Chiralcel AD-H, 208C, 254 nm, 99/1
20.65 min.
Acknowledgements
hexane/i-PrOH, 1.0 mLminꢀ1):
tmajor =28.27 min, tminor =
We are grateful for financial support from the Chinese Acad-
emy of Sciences and National Natural Science Foundation of
China (20873166 and 21073210).
24.86 min.
trans-(2S,3R)-Epoxy-3-(4-fluorophenyl)-1-phenylpropan-
1
1-one: Yield: 73%; H NMR (400 MHz, CDCl3): d=8.00 (d,
J=8.4 Hz, 2H, ArH), 7.63 (t, J=7.6 Hz, 1H, ArH), 7.49 (t,
J=8.0 Hz, 2H, ArH), 7.37–7.33 (m, 2H, ArH), 7.09 (t, J=
8.4 Hz, 2H, ArH), 4.25 (d, J=2.0 Hz, 1H, CH), 4.07 (d, J=
2.0 Hz, 1H, CH); 13C NMR (100 MHz, CDCl3): d=192.9,
164.4, 161.9, 135.4, 134.1, 131.3, 131.2, 128.9, 128.4, 127.6,
127.5, 116.0, 115.8, 60.9, 58.8; HPLC (Chiralcel OJ, 208C,
References
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254 nm, 90/10 hexane/i-PrOH, 1.0 mLminꢀ1): tmajor
17.46 min, tminor =20.65 min.
=
trans-(2S,3R)-Epoxy-3-(4-methylphenyl)-1-phenylpropan-
1
1-one: Yield: 52%; H NMR (400 MHz, CDCl3): d=8.00 (d,
J=6.8 Hz, 2H, ArH), 7.61 (t, J=7.6 Hz, 1H, ArH), 7.49 (t,
J=7.6 Hz, 2H, ArH), 7.28–7.21(m, 4H, ArH), 4.30 (d, J=
1.6 Hz, 1H, CH), 4.04 (d, J=1.6 Hz, 1H, CH), 2.38 (s, 3H,
CH3); 13C NMR (100 MHz, CDCl3): d=193.2, 139.1, 136.0,
134.0, 132.4, 129.5, 128.9, 128.3, 125.8, 61.1, 59.5, 21.3;
HPLC (Chiralcel OD-H, 208C, 254 nm, 98/2 hexane/i-
PrOH, 1.0 mLminꢀ1): tmajor =17.58 min, tminor =18.78 min.
trans-(2S,3R)-Epoxy-3-phenyl-1-(4-chlorophenyl)-propan-
1
1-one: Yield: 40%; H NMR (400 MHz, CDCl3): d=7.97 (d,
J=8.8 Hz, 2H, ArH), 7.47 (d, J=8.8 Hz, 2H, ArH), 7.44–
7.35 (m, 5H, ArH), 4.25 (d, J=2.0 Hz, 1H, CH), 4.08 (d, J=
2.0 Hz, 1H, CH); 13C NMR (100 MHz, CDCl3): d=192.1,
140.6, 135.2, 133.7, 129.8, 129.3, 129.2, 128.8, 125.8, 61.1,
59.4. HPLC (Chiralcel OJ, 208C, 254 nm, 90/10 hexane/i-
PrOH, 1.0 mLminꢀ1): tmajor =23.02 min, tminor =18.70 min.
trans-Epoxy-3-phenyl-1-(4-fluorophenyl)-propan-1-one:
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Marchi-Delapierre, A. Jorge-Robin, A. Thibon, S.
1
Yield: 56%; H NMR (400 MHz, CDCl3): d=8.09–8.04 (m,
2H, ArH), 7.44–7.36 (m, 5H, ArH), 7.17 (t, J=8.4 Hz, 2H,
ArH), 4.25 (d, J=1.6 Hz, 1H, CH), 4.08 (d, J=1.6 Hz, 1H,
CH); 13C NMR (100 MHz, CDCl3): d=191.6, 167.5, 165.0,
135.3, 131.9, 131.8, 131.2, 131.1, 129.2, 128.8, 125.8, 116.3,
116.0, 61.1, 59.3; HPLC (Chiralcel AD-H, 208C, 254 nm, 90/
Adv. Synth. Catal. 2011, 353, 3014 – 3022
ꢃ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3021