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This chapter presents recent developments regarding lithium, sodium, and potassium salt-based catalysis, with a particular focus on asymmetric catalysis involving carbon–carbon bond formation. While these alkali-metal salts have traditionally been recognised as simple Brønsted or Lewis bases, there have recently been tremendous advances based in chiral cooperative functional acid–base catalysts, such as chiral crown–alkali-metal complexes, chiral lanthanoid/alkali-metal complexes, chiral alkali-metal alkoxides, and chiral alkali-metal phosphates. This chapter describes a variety of recent synergic acid–base catalyst systems for highly efficient transformations that have not previously been possible with the use of conventional catalysts that rely only on Lewis acidity or Brønsted/Lewis basicity.

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