Allylic Isomerizing or Derivatizing Reactions of Organoalanes

Since the preparation and properties of unsaturated organoaluminum compounds have been the subject of a recent critical review (62), attention will be directed here to newer evidence bearing on allylic structure and its benzylic analogs. Examination of the NMR spectra of 

Since some unsolvated allylic systems exhibit such facile rearrangement, it is evident that Lewis bases may drive the equilibrium toward one form by preferential coordination [Eq. (34)]. If the relative stabilities 

On the other hand, to anticipate the discussion in Section IV,B and show how misleading hydrolysis products can be, consider the case of diethyl(3-phenyl-2-propen-l-yl)aluminum etherate (76), whose structure 

Furthermore, the 1-acenaphthenylaluminum system (67), possessing a more reactive aromatic system, was found to respond most readily to various reagents to give extensive amounts of rearrangement products (25-27). Significantly, with this system both kinetic and thermodynamic 

The Influence of Donors on the Proportions of 1,3-Dihydroacenaphthylene and Acenaphthene Formed in the Hydrolysis of 1-Acenaphthenyl(diisobutyl)aluminum (67)  

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