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33746539633
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note
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Due to the two-phase character of the reaction, severe explosions may occur when PhI(N3)2 is generated from iodosobenzene (PhIO). In our experience, this problem can be avoided when (diacetoxyiodo)benzene is employed instead.
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25
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For other examples of the selective reduction of 2,3-dihydro-4//pyran-4-ones see: K. J. Hale, and S. Manaviazar, Tetrahedron Lett., 1994, 35, 8873; T. Nakata, H. Matsukura, D. Jian, and H. Nagashima, Tetrahedron Lett., 1994, 35, 8229; A. Golebiowski, and J. Jurczak, Tetrahedron, 1991, 47, 1045; S. Danishefsky, S. Kobayashi, and J. F. Kerwin, Jr., J. Org. Client., 1982,47, 1883.
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The Luche reduction "did also not work with other 4-O-silyIated glycals such as compounds 11 or 14. Herscovici et al. applied the Luche reduction to similar enones, quoting much higher selectivities for //ireo-configured pyranones. However, we were unable to repeat their results: J. Herscovici, R. Montserret, and K. Astonakis, Carbohydr. Res., 1988, 176, 219. When the substituent at C-4 (carbohydrate numbering) is missing, the Luche reduction is governed by the substituent at C-5, exclusively, leading to the corresponding //wo-products: D. Meng, P. Bertinato, A. Balog, D.-S. Su, T. Kamenecka, E. J. Sorensen, and S. J. Danishefsky, J. Ant. Chem. Soc., 1997,119, 10073, and réf. 26.
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Et Al. Applied the Luche Reduction to Similar Enones, Quoting Much Higher Selectivities for //Ireo-configured Pyranones. However, We Were Unable to Repeat Their Results: J. Herscovici, R. Montserret, and K. Astonakis, Carbohydr. Res.
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3, DEAD, itetramethylguanidinium azide, and acetic acid, did not lead to incorporation of azide.
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