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The Behaviour of a Dialuminoxane and Distannoxanes towards Organic Molecules

  • Hitosi Nozaki
  • Junzo Otera
Conference paper

Abstract

The concept of the combined acid-base attack is exemplified by the behaviour of organoaluminium amides towards trisubstituted oxiranes, which are converted into allylic alcohols. The coordination of the reagent on the oxirane oxygen occurs in a fast equilibrium, whereas the nitrogen lone pair thus activated abstracts a proton from the ∝-carbon on the same side as the ring hydrogen, and the nucleophilic attack is rate-and product-determining. Furthermore, the above concept is extended to the reaction of neryl diethyl phosphate with (iBu2Al) 2O, which involves the intermediary ion-pair containing neryl cation and phosphate-dialuminoxane complex anion. The extensively delocalized negative charge in the anion complex leaves a nearly naked neryl carbocation behind, the cyclization of which is followed by deprotonation. The latter stage of nucleophilic attack is again the real rate and product-determining step. The concept of the combined acid-base attack is exemplified by the behaviour of organoaluminium amides towards trisubstituted oxiranes, which are converted into allylic alcohols. The coordination of the reagent on the oxirane oxygen occurs in a fast equilibrium, whereas the nitrogen lone pair thus activated abstracts a proton from the oc-carbon on the same side as the ring hydrogen, and the nucleophilic attack is rate-and product-determining. Furthermore, the above concept is extended to the reaction of neryl diethyl phosphate with (iBu2Al)20, which involves the intermediary ion-pair containing neryl cation and phosphate-dialuminoxane complex anion. The extensively delocalized negative charge in the anion complex leaves a nearly naked neryl carbocation behind, the cyclization of which is followed by deprotonation. The latter stage of nucleophilic attack is again the real rate- and product-determining step.

Keywords

Nucleophilic Attack Allylic Alcohol Nitrogen Lone Pair Fast Equilibrium Oxirane Oxygen 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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Copyright information

© Springer-Verlag Berlin Heidelberg 1988

Authors and Affiliations

  • Hitosi Nozaki
    • 1
  • Junzo Otera
    • 1
  1. 1.Department of Applied ChemistryOkayama University of ScienceOkayamaJapan

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