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30.0, 28.6, 28.5, 28.3, 27.6, 26.5, 26.3, 24.3, 24.2, 23.5, 23.2, 22.9, 22.8,
21.2, 21.1, 18.6, 18.1, 18.0, 17.3; MS 169 (M + H+, 18).
(4) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Tetrahedron
Lett. 1990, 31, 7345−7348.
5,10-Dioxatricyclo[7.1.0.04,6]decane (2p):38 colorless oil; 137
(5) For examples, see: (a) Adolfsson, H.; Coperet, C.; Chiang, J. P.;
Yudin, A. K. J. Org. Chem. 2000, 65, 8651−8658. Ru-catalyzed
epoxidation: (b) Zhang, J.-L.; Che, C.-M. Chem.Eur. J. 2005, 11,
3899−3914. V-catalyzed epoxidation: (c) Nakagawa, Y.; Kamata, K.;
Kotani, M.; Yamaguchi, K.; Mizuno, N. Angew. Chem., Int. Ed. 2005,
44, 5136−5141. Mo-catalyzed epoxidation: (d) Barlan, A. U.; Basak,
A.; Yamamoto, H. Angew. Chem., Int. Ed. 2006, 45, 5849−5852. Ti-
catalyzed epoxidation: (e) Sawada, Y.; Matsumoto, K.; Katsuki, T.
Angew. Chem., Int. Ed. 2007, 46, 4559−4561. Fe-catalyzed
epoxidation: (f) Bruijnincz, P. C. A.; Buurmans, I. L. C.; Gosiewska,
S.; Moelands, M. A. H.; Lutz, M.; Spek, A. L.; van Koten, G.; Klein
Gebbink, R. J. M. Chem.Eur. J. 2008, 14, 1228−1237. (g) Liu, P.;
Wong, E. L.-M.; Yuen, A. W.-H.; Che, C.-M. Org. Lett. 2008, 10,
3275−3278. W-catalyzed epoxidation: (h) Kamata, K.; Sugahara, K.;
Yonehara, K.; Ishimoto, R.; Mizuno, N. Chem.Eur. J. 2011, 17,
7549−7555.
1
mg, 98% yield; H NMR (200 MHz, CDCl3) δ 3.05−2.95 (4H, m),
2.04−1.82 (8H, m); 13C (50 MHz, CDCl3) δ 56.1, 21.9; MS 141 (M +
H+, 52).
3-(Oxiran-2-yl)-7-oxabicyclo[4.1.0]heptane (2q):39 colorless
oil; 123 mg, 88% yield; mixture of four diastereomers; 1H NMR
(200 MHz, CDCl3) δ 3.24−3.14 (2H, m), 2.80−2.66 (2H, m), 2.55−
2.46 (1H, m), 2.28−1.08 (7H, m); 13C (50 MHz, CDCl3) δ 56.0, 55.7,
55.6, 55.5, 52.5, 52.4, 52.3, 52.2, 51.7, 51.6, 50.9, 50.8, 46.3, 46.2, 45.7,
45.4, 35.7, 35.2, 32.7, 31.9, 27.4, 27.2, 27.0, 25.8, 24.3, 24.1, 23.6, 23.2,
22.9, 22.7, 21.4, 20.2; MS 141 (M + H+, 37).
1-(Oxiran-2-yl)ethanone (2r):40 colorless oil; 84 mg, 98% yield;
1H NMR (200 MHz, CDCl3) δ 3.38 (1H, dd, J = 4.6 and 2.5 Hz), 3.01
(1H, dd, J = 5.7 and 4.6 Hz), 2.88 (1H, dd, J = 5.7 and 2.5 Hz), 2.02
(3H, s); 13C (50 MHz, CDCl3) δ 205.8, 53.8, 45.8, 23.7; MS 86 (M+,
21).
7-Oxabicyclo[4.1.0]heptan-2-one (2s):5h colorless oil; 111 mg,
(6) For books, see: (a) Berkessel, A., Groger, H. In Asymmetric
Organocatalysis − From Biomimetic Concepts to Powerful Methods for
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1
99% yield; H NMR (200 MHz, CDCl3) δ 3.66−3.54 (1H, m), 3.26
(1H, d, J = 4.0 Hz), 2.63−2.48 (1H, m), 2.33−2.19 (1H, m), 2.12−
1.88 (3H, m), 1.71−1.66 (1H, m); 13C (50 MHz, CDCl3) δ 205.7,
55.8, 55.0, 36.1, 22.7, 16.9; MS 112 (M+, 11).
(6aS,6bS,9R,9aR,11aS,11bR)-9a,11b-Dimethyl-9-((R)-6-meth-
ylheptan-2-yl)hexadecahydrocyclopenta[1,2]phenanthro-
[8a,9-b]oxiren-3-ol (2t):41 white solid; mp 132−134 °C; 395 mg,
1
98% yield; mixture of diastereomers (60:40); H NMR (200 MHz,
CDCl3) δ 4.01−3.81 (0.4H, m), 3.79−3.61 (0.6H, m), 3.07 (0.6H, d, J
= 2.1 Hz), 2.92 (0.4H, d, J = 4.4 Hz), 2.42 (1H, br s), 2.22−1.70 (6H,
m), 1.70−0.78 (22H, m), 1.03 (1.2H, s), 0.96 (1.8H, s), 0.89 (1.2H,
s), 0.87 (1.2H, s), 0.85 (3.6H, s), 0.82 (3H, s), 0.61 (1.8H, s), 0.58
(1.2H, s); 13C (50 MHz, CDCl3) δ 69.4, 68.7, 66.5, 64.2, 63.6, 59.8,
57.0, 56.4, 56.3, 56.0, 51.5, 42.7, 42.5, 42.4, 42.1, 39.9, 39.6, 39.5, 39.4,
37.4, 36.3, 35.9, 34.9, 34.8, 32.7, 32.6, 30.9, 29.9, 29.8, 28.9, 28.4, 28.3,
28.2, 28.0, 24.4, 24.2, 24.0, 23.6, 23.0, 22.8, 22.2, 20.8, 18.8, 17.1, 16.1,
12.1, 12.0; MS 403 (M + H+, 19).
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ASSOCIATED CONTENT
* Supporting Information
■
S
General remarks, catalyst and conditions optimization including
NMR data, as well as mechanistic investigations. This material
AUTHOR INFORMATION
Corresponding Author
■
(11) (a) Tu, Y.; Wang, Z.-X.; Shi, Y. J. Am. Chem. Soc. 1996, 118,
9806−9807. (b) Wang, Z.-X.; Tu, Y.; Frohn, M.; Zhang, J.-R.; Shi, Y. J.
Am. Chem. Soc. 1997, 119, 11224−11225. (c) Shu, L.; Shi, Y.
Tetrahedron Lett. 1999, 40, 8721−8724. (d) Tian, H.; She, X.; Yu, H.;
Shu, L.; Shi, Y. J. Org. Chem. 2002, 67, 2435−2446. (e) Burke, C. P.;
Shi, Y. Org. Lett. 2009, 11, 5150−5153.
(12) (a) Peris, G.; Jakobsche, C. E.; Miller, S. J. J. Am. Chem. Soc.
2007, 129, 8710−8711. (b) Mello, R.; Alcalde-Aragones, A.; Olmos,
A.; Gonzalez-Nunez, M. E.; Asensio, G. J. Org. Chem. 2012, 77, 4706−
4710.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We gratefully acknowledge the Operational Program “Educa-
tion and Lifelong Learning” for financial support through the
NSRF program “ENIΣXYΣH METAΔIΔAKTOPΩN
EPEYNHTΩN” (PE 2431) cofinanced by ESF and the Greek
State.
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Fusco, C.; Lattanzi, A. ChemCatChem 2012, 4, 901−916. (c) Lee, A.;
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(d) Capobianco, A.; Russo, A.; Lattanzi, A.; Peluso, A. Adv. Synth.
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F.; Neudorfl, J.-M.; Haag, R. Angew. Chem., Int. Ed. 2013, 452, 739−
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