Practical Corey-Chaykovsky Epoxidation
Letters in Organic Chemistry, 2011, Vol. 8, No. 7
513
2,2-Diphenyloxirane (2a)
5.6 Hz, 1H in CH2). 13C NMR (75.5 MHz, CDCl3) ꢀ: 50.8,
52.0, 125.8, 128.0, 128.3, 138.0.
Colorless crystals (1.901 g, 97%); mp 55–56 °C; Lit [21].
mp 55–56 °C. 1H NMR (300 MHz, CDCl3) ꢀ: 7.23–7.16 (m,
10H, ArH), 3.12 (s, 2H, CH2). 13C NMR (75.5 MHz, CDCl3)
ꢀ: 56.6, 61.8, 127.7, 128.0, 128.2, 140.6.
(E)-Cinnamenyl methyl ether [41]
1
Colorless oil (74 mg, 5%); H NMR (300 MHz, CDCl3)
ꢀ: 7.40–7.24 (m, 5H, ArH), 6.65 (dt, J = 15.9, 1.5 Hz, 1H,
CH), 6.27 (dt, J = 15.9, 6.0 Hz, 1H, CH2), 4.08 (dd, J = 1.5,
6.0 Hz, 2H, CH2), 3.37 (s, 3H, CH3). 13C NMR (75.5 MHz,
CDCl3) ꢀ: 55.7, 106.0, 125.0, 125.2, 128.2, 136.3, 148.1.
2-(4-Methylphenyl)-2-phenyloxirane (2b) [35]
Colorless oil (2.079 g, 99%); 1H NMR (300 MHz,
CDCl3) ꢀ: 7.35–7.13 (m, 9H, ArH), 3.29 (d, J = 5.4 Hz, 1H
in CH2), 3.25 (d, J = 5.4 Hz, 1H in CH2), 2.35 (s, 3H, CH3).
13C NMR (75.5 MHz, CDCl3) ꢀ: 21.7, 56.8, 62.0, 127.8,
128.1, 128.4, 140.5.
Methyl 4-methylphenyl ether [42]
1
Colorless oil (61 mg, 5%); H NMR (300 MHz, CDCl3)
ꢀ: 7.13–7.02 (m, 4H, ArH), 4.36 (s, 2H, CH2), 3.31 (s, 3H,
CH2), 2.31 (s, 3H, CH3). 13C NMR (75.5 MHz, CDCl3) ꢀ:
20.4, 54.5, 114.0, 129.8, 130.0, 158.0.
2-Methyl-2-phenyloxirane (2c) [21]
Colorless oil (1.018 g, 76%); 1H NMR (300 MHz,
CDCl3) ꢀ: 7.29–7.17 (m, 5H, ArH), 2.90 (d, J = 5.4 Hz, 1H
in CH2), 2.80 (dq, J = 5.4, 0.6 Hz, 1H in CH2), 1.72 (d, J =
0.6 Hz, 3H, CH3). 13C NMR (75.5 MHz, CDCl3) ꢀ: 22.0,
57.0, 57.3, 125.8, 127.9, 128.2, 141.9.
ACKNOWLEDGEMENTS
This work was supported by the National Natural Science
Foundation of China (Project No. 20772005) and Beijing
Natural Science Foundation (Project No. 2092022).
2-Ethyl-2-phenyloxirane (2d) [25]
Colorless oil (1.051 g, 71%); 1H NMR (300 MHz,
CDCl3) ꢀ: 7.38–7.26 (m, 5H, ArH), 2.97 (d, J = 5.4 Hz, 1H
in CH2), 2.80 (d, J = 5.4 Hz, 1H in CH2), 2.19 (dq, J = 14.5,
7.5 Hz, 1H in CH2), 1.79 (dq, J = 14.5, 7.5 Hz, 1H in CH2),
0.94 (t, J = 7.5 Hz, 3H, CH3). 13C NMR (75.5 MHz, CDCl3)
ꢀ: 9.2, 28.5, 55.7, 66.2, 126.2, 127.5, 128.5, 140.3.
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2-Methyl-2-pentyloxirane (2e) [36]
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Li, J.J. Epoxides and Aziridines. Corey-Chaykovsky reaction. In:
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reagent for selective oxirane synthesis from aldehydes and ketones.
J. Am. Chem. Soc. 1962, 84, 3782-3783.
Colorless oil (563 mg, 44%); 1H NMR (300 MHz,
CDCl3) ꢀ: 2.60 (d, J = 5.4 Hz, 1H in CH2), 2.59 (d, J = 4.8
Hz, 1H in CH2), 1.63–1.20 (m, 8H, 4CH2), 1.30 (s, 3H,
CH3), 0.89 (t, J = 6.8 Hz, 3H, CH3). 13C NMR (75.5 MHz,
CDCl3) ꢀ: 57.0, 53.9, 36.6, 31.7, 24.8, 22.5, 20.8, 13.9.
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2,2-Dipropyloxirane (2f) [37]
Colorless oil (397 mg, 31%); 1H NMR (300 MHz,
CDCl3) ꢀ: 2.58 (s, 2H, CH2), 1.64–1.30 (m, 8H, 4CH2), 0.93
(t, J = 6.8 Hz, 3H, CH3), 0.92 (t, J = 6.8 Hz, 3H, CH3). 13C
NMR (75.5 MHz, CDCl3) ꢀ: 14.2, 18.7, 39.0, 53.5, 56.5.
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2-(4-Methylphenyl)oxirane (2g) [38]
Colorless oil (671 mg, 50%); 1H NMR (300 MHz,
CDCl3) ꢀ: 7.33–7.07 (m, 4H, ArH), 3.81 (dd, J = 2.4, 4.2 Hz,
1H, CH), 3.10 (dd, J = 4.2, 5.4 Hz, 1H in CH2), 2.77 (dd, J =
2.4, 5.4 Hz, 1H in CH2), 2.33 (s, 3H, CH3). 13C NMR (75.5
MHz, CDCl3) ꢀ: 21.9, 50.2, 52.0, 125.8, 128.9, 134.3, 137.3.
[10]
[11]
[12]
2-(1-Naphthyl)oxirane (2h) [39]
1
Colorless crystals (765 mg, 45%); H NMR (300 MHz,
CDCl3) ꢀ: 8.09 (m, 1H, ArH), 7.90–7.81 (m, 2H, ArH),
7.61–7.36 (m, 4H, ArH), 4.10 (dd, J = 2.7, 4.2 Hz, 1H, CH),
3.20 (dd, J = 4.2, 5.4 Hz, 1H in CH2), 2.84 (dd, J = 2.7, 5.4
Hz, 1H in CH2). 13C NMR (75.5 MHz, CDCl3) ꢀ: 50.9, 52.2,
123.3, 123.5, 125.3, 125.9, 126.1, 127.8, 128.7, 131.2, 133.1,
134.0.
[13]
[14]
[15]
[16]
2-Phenyloxirane (2j) [40]
1
Colorless oil (72 mg, 6%); H NMR (300 MHz, CDCl3)
ꢀ: 7.36–7.26 (m, 5H, ArH), 3.83 (dd, J = 2.6, 4.1 Hz, 1H,
CH), 3.11 (dd, J = 4.1, 5.6 Hz, 1H in CH2), 2.78 (dd, J = 2.6,