Allylic rearrangement

Stereocenter

Organic chemistry

Combinatorial chemistry

Tsuji–Trost reaction

Stereochemistry

Transition metal

Enantioselective synthesis

Catalysis

Nucleophile

Alkylation

Chemistry

Chemical Reviews

Asymmetric allylic alkylation mediated by transition metals provides an efficient strategy to form quaternary stereogenic centers. While this transformation is dominated by the use of second- and third-row transition metals (e.g., Pd, Rh, and Ir), recent developments have revealed the potential of first-row transition metals, which provide not only a less expensive and potentially equally efficient alternative but also new mechanistic possibilities. This review summarizes examples for the assembly of quaternary stereocenters using prochiral allylic substrates and hard, achiral nucleophiles in the presence of copper complexes and highlights the complementary approaches with soft, prochiral nucleophiles catalyzed by chiral cobalt and nickel complexes.

Enantioselective Formation of Quaternary Centers by Allylic Alkylation with First-Row Transition-Metal Catalysts