Toward asymmetric aldol-Tishchenko reactions with enolizable aldehydes: access to defined configured stereotriads, tetrads, and stereopentads.

Asymmetric aldol-Tishchenko reactions of enolizable aldehydes and ketones in the presence of chiral BINOLTi(OtBu)(2)/cinchona alkaloids complexes are described. Different configurative outcomes of these reactions depend on an equilibration through a retro aldol/aldol sequence and can be influenced by the configurative architecture of substrates. The results are explained by means of transition state models and rate constants. These considerations offer a fine-tuning of diastereoselectivity in aldol-Tishchenko reactions. Extensions of this research give access to defined configured stereotriads, stereotetrads, and stereopentads.