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We should note the difference in the reactivities between ketone enolates and ester enolates, though they are often treated without distinction.
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The subsequent step such as cyclization after Michael addition contributes to the stabilization of the product system: (a) Miller, J. J.; de Benneville, P. L. J. Org. Chem. 1957, 22, 1268-1269.
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0001960224
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Organotin enolates exist as equilibrium mixtures of keto- and/or enol forms; 1e and 1c exclusively exist in keto and enol forms, respectively: Pereyre, M.; Bellegarde, B.; Mendelsohn, J.; Valade, J. J. Organomet. Chem. 1968, 11, 97-110.
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Enol forms generally show higher reactivity than keto forms: Kobayashi, K.; Kawanisi, M.; Hitomi, T.; Kozima, S. Chem. Lett. 1983, 851-854. The low yield in the reaction of keto form enolate was probably caused by thermodynamic factors.
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For the organotin ester enolates, the equilibrium between O-stannylated and C-stannylated forms generally lies to the C-stannylated species above O°C. Shimada, E.; Inomata, K.; Mukaiyama, T. Chem. Lett. 1974, 689-690.
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The fluoride anion catalyzed-Michael addition of ketene silyl acetals to enones has been reported, showing a similar highly coordinated silicon species. RajanBabu, T. V. J. Org. Chem. 1984, 49, 2083-2089.
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40
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0345108344
-
-
note
-
The coordination by bromide anion suppresses the carbonyl addition of the tin enolate (ref 20a).
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