Felkin规则和Cram规则 不对称诱导(5)

However, in the case of the syn-substrate, the Felkin–Anh and the Evans model predict different products (non-stereoreinforcing case). It has been found that the size of the incoming nucleophile determines the type of control exerted over the stereochemistry. In the case of a large nucleophile, the interaction of the α-stereocenter with the incoming nucleophile becomes dominant; therefore, the Felkin product is major one. Smaller nucleophiles, on the other hand, result in 1,3 control determining the asymmetry.[21]

Acyclic alkenes asymmetric induction[edit]

Chiral acyclic alkenes also show diastereoselectivity upon reactions such as epoxidation and enolate alkylation. The substituents around the alkene can favour the approach of the electrophile from one or the other face of the molecule. This is the basis of the Houk's model, based on

theoretical work by Kendall Houk, which predicts that the selectivity is stronger for cis than for trans double bonds.[22]

In the example shown, the cis alkene assumes the shown conformation to minimize steric clash between RS and the methyl group. The approach of the electrophile preferentially occurs from the same side of the medium group (RM) rather than the large group (RL), mainly producing the shown diastereoisomer. Since for a trans alkene the steric hindrance between RS and the H group is not as large as for the cis case, the selectivity is much lower