ChemInform Abstract: STEREOSELECTIVITY OF THE ADDITION OF CHARGE‐LOCALIZED ANION NUCLEOPHILES TO CYCLOHEXANONES

Abstract

Die Stereoselektivität der Addition der verschiedenen Metallsalze (II), (VII) und (X) an die Cyclohexanone (I) bzw. (XIII) unter verschiedenen Bedingungen wird untersucht.

Inductive and Resonance Effects of Substituents on π-Face Selection

“…However, the large dependence of π-face selectivity on the properties of the solvent is observed only in the case of ester enolates. Thus, the results of alkylation with those enolates are listed separately for the solvating and nonsolvating media, taking this change in solvent properties as equivalent to lowering enolate basicity. − ,− …”

“…Thus, the results of alkylation with those enolates are listed separately for the solvating and nonsolvating media, taking this change in solvent properties as equivalent to lowering enolate basicity. [30][31][32][33][34][35][36][311][312][313][314][315][316][317][318][319][320][321][322][323][324] The data for the secondary and tertiary anions, all obtained in liquid NH 3 (Na + as the counterion), 36 are plotted in Figure 35 against the rank order of reactivity based on the pK a values of the model compounds and the assumption that the pK a values of the cyclic derivatives reflect the ring-size effect on the delocalization of the unshared electron pair. 325 In contrast to the secondary carbanions, the stereochemistry of the addition of the primary and tertiary carbanions appears to strongly depend on their basicity.…”