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For recent examples reported by our group, see: (a) Sakurada, I.; Yamasaki, S.; Göttlich, R.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc. 2000, 122, 1245.
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33
-
-
13944280737
-
-
note
-
3As= O (1:1:1) complex was used.
-
-
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34
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0003164794
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(a) Zhou, Y.-G.; Hou, X.-L.; Dai, L.-X.; Xia, L.-J.; Tang, M-H. J. Chem. Soc., Perkin Trans. 1 1999, 77.
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38
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0001781416
-
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For regioselective epoxide-opening reactions with azide using other Lewis acid catalysts, see: (a) Denis, J.-N.; Green, A. E.; Serra, A. A.; Luche, M.-J. J. Org. Chem. 1986, 51, 46.
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42
-
-
13944266088
-
-
note
-
The syn isomer was contaminated with the anti isomer (anti:syn = 11:1). The moderate overall yield was due to the partial decomposition of the corresponding α,β-epoxy amide during the epoxidation reaction.
-
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44
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0001615493
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(b) Blandy, C.; Choukroun, R.; Gervais, D. Tetrahedron Lett. 1983, 24, 4189.
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-
50
-
-
13944273489
-
-
note
-
3 or (S)-Sm complex 1 resulted in similar IR spectra. For details, see the Supporting Information.
-
-
-
-
51
-
-
13944261314
-
-
note
-
BINOL would not be involved in the samarium azide complex because all of the BINOL was silylated in the reaction mixture.
-
-
-
-
52
-
-
13944260590
-
-
note
-
-1 suggested that the samarium azide complex exists as a mixture of several oligomeric species in equilibrium.
-
-
-
-
53
-
-
13944264776
-
-
note
-
α,β-Epoxy chalcone: no reaction. α,β-Epoxy methyl cinnamate: trace.
-
-
-
-
54
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-
0003412412
-
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For Hammett substituent constants, see: Smith, M. B.; March, J. March's Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, 5th ed.; John Wiley and Sons: New York, 2002.
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Smith, M.B.1
March, J.2
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55
-
-
13944263324
-
-
note
-
The catalytic asymmetric epoxidation of α,β-unsaturated N-acylimidazolides or α,β-unsaturated ketones would proceed easily because of their low enough LUMO energy level and thus would not require the Lewis base enhancements.
-
-
-
-
56
-
-
13944267615
-
-
note
-
The initial rate of step A should be increased as the LUMO energy level decreased (6a → 6e) if the effects of Lewis basicity of carbonyl moiety were ignored. As observed in the Hammett plot of Scheme 3, the range of the initial rate of step A was smaller than that of step B, where only the Lewis basicity defines the reactivity.
-
-
-
-
57
-
-
0037013975
-
-
For other examples of the superiority of α,β-unsaturated amides to α,β-unsaturated esters in terms of reactivity, see: (a) Concellón, José M.; Rodríguez-Solla, H.; Gómez, C. Angew. Chem., Int. Ed. 2002, 41, 1917.
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Concellón José, M.1
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58
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0242321238
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(b) Kamimura, A.; Murakami, N.; Kawahara, F.; Yokota, K.; Omata, Y.; Matsuura, K.; Oishi, Y.; Morita, R.; Mitsudera, H.; Suzukawa, H.; Kakehi, A.; Shirai, M.; Okamoto, H. Tetrahedron 2003, 59, 9537.
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Kamimura, A.1
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Oishi, Y.7
Morita, R.8
Mitsudera, H.9
Suzukawa, H.10
Kakehi, A.11
Shirai, M.12
Okamoto, H.13
-
59
-
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0001699856
-
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Azide groups can act as bridging ligands between metal atoms leading to di- and polynuclear complexes. For selected examples, see: (a) Fehlhammer, W. P.; Dahl, L. F. J. Am. Chem. Soc. 1972, 94, 3377.
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(c) Goher, M. A. S.; Al-Salem, N. A.; Mautner, F. A.; Klepp, K. O. Polyhedron 1997, 16, 825.
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84955828127
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(d) Clegg, W.; Krischner, H.; Saracoglu, A. I.; Sheldrick, G. M. Z. Kristallogr. 1982, 161, 307. On the basis of the large coordination numbers of lanthanide metals, the samarium azide complex might contain an azido-bridging structure to form the oligomer.
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Clegg, W.1
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-
63
-
-
13944270725
-
-
note
-
9a was obtained in 75% yield after 48 h.
-
-
-
-
64
-
-
13944277210
-
-
note
-
Tertiary amides gave the epoxide-opened products with low regioselectivity (ca. 1:1) although the reaction proceeded smoothly under the same reaction conditions. For the difference of the regioselectivity between secondary and tertiary amides, see ref 12.
-
-
-
-
65
-
-
13944280374
-
-
note
-
Less than 10% of the oxidized product was formed. When sulfide 9a was subjected to conditions for the catalytic asymmetric epoxidation [(S)-Sm complex 1 (10 mol %), TBHP (1.2 equiv), THF, room temperature], a complex mixture of oxidized products was obtained.
-
-
-
-
66
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0034697199
-
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For reviews of asymmetric synthesis of vicinal amino alcohols, see: (a) Bergmeire, S. C. Tetrahedron 2000, 56, 2561.
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Bergmeire, S.C.1
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0001030240
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Beller, M., Bolm, C., Eds.; Wiley-VCH: Weinheim, Germany
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Kolb, H.C.1
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For synthesis of taxol from baccatin III. see: (d) Kingston, D. G. I.; Chaudhary, A. G.; Gunatilaka, A. A. L.; Middleton, M. L. Tetrahedron Lett. 1994, 35, 4483.
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