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Zum Mechanismus der Carbodesilylierung 4- bzw. 5-substituierter 2-(Trimethylsilyl)pyridine mit Benzaldehyd

✍ Scribed by Effenberger, Franz ;Krebs, Andreas ;Willrett, Peter


Publisher
Wiley (John Wiley & Sons)
Year
1992
Tongue
English
Weight
967 KB
Volume
125
Category
Article
ISSN
0009-2940

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✦ Synopsis


An ..ylide mechanism" is proposed for the carbodesilylation of 2-(trimethylsily1)pyridines with benzaldehyde. In contrast, 3and 4-(trimethylsilyl)pyridines, react only in the presence of a base catalyst via pyridyl anions with electrophiles. The rates of the uncatalyzed carbodesilylation reactions of 4-substituted 2-(trimethylsily1)pyridines 2 with benzaldehyde correlate very well with the resonance parameters of the substituents &, whereas the rates of 5-substituted 2-(trimethylsily1)pyridines 7 correlate with the inductive substituent parameters o1 in the Taft equation. This is to our knowledge the first direct determination of the resonance parameters &.


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