Abstract
<jats:title>Abstract</jats:title> <jats:p>This chapter emphasizes the progress and development of transition metal‐catalyzed allylic alkylations for enantioselective and diastereoselective carbon‐carbon bond formations by using preformed lithium enolates of various carbonyl and carboxyl derivatives. The protocol for the synthesis of (R)‐ and (S)‐2‐allylcyclohexanone had been chosen for demonstrating that preformed, non‐stabilized lithium enolates are suitable nucleophiles for palladium‐catalyzed asymmetric allylic alkylations. This method is a direct alternative to the intramolecular variant, the decarboxylative asymmetric allylic alkylation that starts from allyl ‐ketoesters or allyl enol carbonates. More fragile and sensitive than enolates of ketones, aldehydes, amides, lactams and lactones are lithium enolates of carboxylic esters that are thermally labile and tend to decompose under formation of ketene and alkoxide. The more nucleophilic silyl ketene acetals that function as ester‐enolate equivalents were used in asymmetric allylic alkylations partly without activation under palladium, copper, or iridium catalysis.</jats:p>