C O MMU N I C A T I O N S
Table 1. Asymmetric Epoxidation of Olefins Catalyzed by Ketone
2
Chem. 1992, 57, 4320. (c) Jacobsen, E. N.; Deng, L.; Furukawa, Y.;
Martinez, L. E. Tetrahedron 1994, 50, 4323.
a
(
4) For recent examples of asymmetric epoxidation of enones see: (a) Enders,
D.; Zhu, J.; Raabe, G. Angew. Chem., Int. Ed. Engl. 1996, 35, 1725. (b)
Elston, C. L.; Jackson, R. F. W.; MacDonald, S. J. F.; Murray, P. J. Angew.
Chem., Int. Ed. Engl. 1997, 36, 410. (c) Bougauchi, M.; Watanabe, S.;
Arai, T.; Sasai, H.; Shibasaki, M. J. Am. Chem. Soc. 1997, 119, 2329. (d)
Bentley, P. A.; Bergeron, S.; Cappi, M. W.; Hibbs, D. E.; Hursthouse,
M. B.; Nugent, T. C.; Pulido, R.; Roberts, S. M.; Wu, L. E. J. Chem.
Soc., Chem. Commun. 1997, 739. (e) Lygo, B.; Wainwright, P. G.
Tetrahedron Lett. 1998, 39, 1599. (f) Arai, S.; Tsuge, H.; Shioiri, T.
Tetrahedron Lett. 1998, 39, 7563. (g) Corey, E. J.; Zhang, F.-Y. Org.
Lett. 1999, 1, 1287. (h) Yu, H.-B.; Zheng, X.-F.; Lin, Z.-M.; Hu, Q.-S.;
Huang, W.-S.; Pu, L. J. Org. Chem. 1999, 64, 8149. (i) Berkessel, A.;
Gasch, N.; Glaubitz, K.; Koch, C. Org. Lett. 2001, 3, 3839. (j) Adam,
W.; Rao, P. B.; Degen, H.-G.; Levai, A.; Patonay, T.; Saha-M o¨ ller, C. R.
J. Org. Chem. 2002, 67, 259.
(
5) Nemoto, T.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123,
9474.
(
6) For general leading references on dioxiranes see: (a) Adam, W.; Curci,
R.; Edwards, J. O. Acc. Chem. Res. 1989, 22, 205. (b) Murray, R. W.
Chem. ReV. 1989, 89, 1187. (c) Curci, R.; Dinoi, A.; Rubino, M. F. Pure
Appl. Chem. 1995, 67, 811. (d) Clennan, E. L. Trends Org. Chem. 1995,
5, 231.
(7) For reviews see: (a) Denmark, S. E.; Wu, Z. Synlett 1999, 847. (b) Frohn,
M.; Shi, Y. Synthesis 2000, 1979.
(
8) For leading references see: (a) Curci, R.; Fiorentino, M.; Serio, M. R. J.
Chem. Soc., Chem. Commun. 1984, 155. (b) Curci, R.; D’Accolti, L.;
Fiorentino, M.; Rosa, A. Tetrahedron Lett. 1995, 36, 5831. (c) Denmark,
S. E.; Forbes, D. C.; Hays, D. S.; DePue, J. S.; Wilde, R. G. J. Org.
Chem. 1995, 60, 1391. (d) Brown, D. S.; Marples, B. A.; Smith, P.;
Walton, L Tetrahedron 1995, 51, 3587. (e) Yang, D.; Yip, Y. C.; Tang,
M. W.; Wong, M. K.; Zheng, J. H.; Cheung, K. K. J. Am. Chem. Soc.
1
996, 118, 491. (f) Yang, D.; Wang, X.-C.; Wong, M.-K.; Yip, Y.-C.;
Tang, M.-W. J. Am. Chem. Soc. 1996, 118, 11311. (g) Song, C. E.; Kim,
Y. H.; Lee, K. C.; Lee, S. G.; Jin, B. W. Tetrahedron: Asymmetry 1997,
8
, 2921. (h) Adam, W.; Zhao, C.-G. Tetrahedron: Asymmetry 1997, 8,
3
995. (i) Denmark, S. E.; Wu, Z.; Crudden, C. M.; Matsuhashi, H. J.
Org. Chem. 1997, 62, 8288. (j) Adam, W.; Fell, R. T.; Saha-M o¨ ller, C.
R.; Zhao, C.-G. Tetrahedron: Asymmetry 1998, 9, 397. (k) Armstrong,
A.; Hayter, B. R. Chem. Commun. 1998, 621. (l) Yang, D.; Yip, Y.-C.;
Chen, J.; Cheung, K.-K. J. Am. Chem. Soc. 1998, 120, 7659. (m) Adam,
W.; Saha-M o¨ ller, C. R.; Zhao, C.-G. Tetrahedron: Asymmetry 1999, 10,
2
749. (n) Carnell, A. J.; Johnstone, R. A. W.; Parsy, C. C.; Sanderson,
W. R. Tetrahedron Lett. 1999, 40, 8029. (o) Armstrong, A.; Hayter, B.
R.; Moss, W. O.; Reeves, J. R.; Wailes, J. S. Tetrahedron: Asymmetry
2
000, 11, 2057. (p) Solladie-Cavallo, A.; Bouerat, L. Org. Lett. 2000, 2,
3
531. (q) Solladie-Cavallo, A.; Bouerat, L.; Jierry, L. Eur. J. Org. Chem.
a
All reactions were carried out at 0 °C to room temperature with substrate
2001, 4557. (r) Bortolini, O.; Fogagnolo, M.; Fantin, G.; Maietti, S.;
Medici, A. Tetrahedron: Asymmetry 2001, 12, 1113. (s) Seki, M.;
Furutani, T.; Imashiro, R.; Kuroda, T.; Yamanaka, T.; Harada, N.;
Arakawa, H.; Kusama, M.; Hashiyama, T. Tetrahedron Lett. 2001, 42,
8201. (t) Armstrong, A.; Moss, W. O.; Reeves, J. R. Tetrahedron:
Asymmetry 2001, 12, 2779. (u) Matsumoto, K.; Tomioka, K. Tetrhedron
Lett. 2002, 43, 631.
(
1 equiv), ketone (0.20-0.30 equiv), Bu4NHSO4 (0.06 equiv), Oxone (5.0
-4
equiv), and NaHCO3 (15.5 equiv) in CH3CN-aq Na2(EDTA) (4 × 10
M) (1.5:1) and stopped after 24 h. For entry 4, the reaction was run at 0 °C
b
for 12 h. The epoxides were purified by flash chromatography and gave
c
d
satisfactory spectroscopic characterization. 0.30 equiv of ketone used. 0.25
equiv of ketone used. e 0.20 equiv of ketone used. Determined by chiral
f
(
9) Wang, Z.-X.; Shi, Y. J. Org. Chem. 1997, 62, 8622.
g
GC (Chiraldex G-TA). Determined by chiral HPLC (Chiralcel OD).
Determined by chiral HPLC (Chiralpak AD). Determined by chiral HPLC
Chiralcel OJ). Determined by chiral HPLC (Chiralcel OB). Determined
h
i
(10) (a) Tu, Y.; Wang, Z.-X.; Shi, Y. J. Am. Chem. Soc. 1996, 118, 9806. (b)
Wang, Z.-X.; Tu, Y.; Frohn, M.; Zhang, J.-R.; Shi, Y. J. Am. Chem. Soc.
j
k
(
1997, 119, 11224. (c) Tian, H.; She, X.; Shi, Y. Org. Lett. 2001, 3, 715.
1
l
by H NMR shift analysis with Eu(hfc)3. Determined by chiral GC
(
11) For leading references on racemic epoxidation of R,â-unsaturated acid
derivatives using dioxiranes see: (a) Reference 6. (b) Corey, P. F.; Ward,
F. E. J. Org. Chem. 1986, 51, 1925. (c) Adam, W.; Hadjiarapoglou, L.;
Nestler, B. Tetrahedron Lett. 1990, 31, 331. (d) Murray, R. W.; Shiang,
D. L. J. Chem. Soc., Perkin Trans. 2 1990, 349. (e) Yang, D.; Wong,
M.-K.; Yip, Y.-C. J. Org. Chem. 1995, 60, 3887. (f) Murray, R. W.; Singh,
S. Org. Synth. 1996, 74, 91. (g) Yang, D.; Yip, Y.-C.; Tang, M.-W.; Wong,
M.-K.; Cheung, K.-K. J. Org. Chem. 1998, 63, 9888.
(
Chiraldex B-DM). m Determined by comparing the measured optical
rotations with the reported ones.
Acknowledgment. We are grateful to the generous financial
support from the General Medical Sciences of the National Institutes
of Health (GM59705-03), the Camille and Henry Dreyfus Founda-
tion, Alfred P. Sloan Foundation, DuPont, Eli Lilly, and Glaxo-
SmithKline.
(
12) For a review on the Baeyer-Villiger oxidation see: Krow, G. R. Org.
React. 1993, 43, 251.
(13) Ketone 2 was readily prepared from 1 by the selective deketalization
DDQ, CH CN-H O) and acetylation (Ac O, DMAP).
(
3
2
2
Supporting Information Available: Experimental procedure for
the asymmetric epoxidation reaction, the characterization of the ketone
and epoxides, and the data for the determination of the enantiomeric
excess of the epoxides (PDF). This material is available free of charge
via the Internet at http://pubs.acs.org.
(14) The enynes were readily prepared using the Pd-catalyzed alkyne coupling
reaction: Trost, B. M.; Sorum, M. T.; Chan, C.; Harms, A. E.; R u¨ ther,
G. J. Am. Chem. Soc. 1997, 119, 698.
(
15) (a) Cabon, O.; Buisson, D.; Larcheveque, M.; Azerad, R. Tetrahedron:
Asymmetry 1995, 6, 2211. (b) Roux-Schmitt, M.-C.; Seyden-Penne, J.;
Wolfe, S. Tetrahedron 1972, 28, 4965. (c) Yamamoto, M.; Hayashi, M.;
Masaki, M.; Nohira, H. Tetrahedron: Asymmetry 1991, 2, 403. (d) Abidi,
S. L.; Wolfhagen, J. L. J. Org. Chem. 1979, 44, 433. (e) Kimata, K.;
Kobayashi, M.; Hosoya, K.; Araki, T.; Tanaka, N. J. Am. Chem. Soc.
References
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(
(
(
1) For a recent review on asymmetric epoxidation of electron-deficient olefins
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see: Porter, M. J.; Skidmore, J. Chem. Commun. 2000, 1215.
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J. AM. CHEM. SOC.
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